Composition comprising polyion complex particle and oil

ABSTRACT

The present invention relates to a composition, preferably a cosmetic composition, and more preferably a skin cosmetic composition, comprising: (a) at least one particle, comprising at least one cationic polymer and at least one anionic polymer, at least one cationic polymer and at least one amphoteric polymer, at least one anionic polymer and at least one amphoteric polymer, or at least one amphoteric polymer, and at least one non-polymeric acid having two or more pKa values or salt(s) thereof or at least one non-polymeric base having two or more pKb values or salt(s) thereof; (b) at least one oil; and (c) water. The composition according to the present invention is stable, and can have a variety of cosmetic functions. For example, the composition according to the present invention can prepare a film which can have cosmetic effects such as moisturizing due to the oil(s).

TECHNICAL FIELD

The present invention relates to a composition including polyion complexparticles and a film of polyion complex particles, as well as a processfor preparing a film by using polyion complex particles and a use ofpolyion complex particles for preparing a film.

BACKGROUND ART

A polyion complex which is formed with an anionic polymer and a cationicpolymer has already been known.

The use of a film made from a polyion complex for cosmetic purposes isalso proposed by, for example, WO 2013/153678 and JP-A-2014-227389. Thefilm disclosed in WO 2013/153678 and JP-A-2014-227389 can providecertain cosmetic effects.

However, the preparation of the film disclosed in WO 2013/153678 andJP-A-2014-227389 requires a spin coating process which needs a highspeed rotation of a substrate, and therefore, it may be difficult toprepare the film in-situ on a keratin substrate such as skin.

JP-A-2015-107939 discloses the preparation of a film made from a polyioncomplex for cosmetic purposes by spraying a first solution of either ofan anionic polymer and a cationic polymer, and spraying a secondsolution of the other of the anionic polymer and the cationic polymer,on a keratin substance, to mix the anionic and cationic polymers to forma film including the polyion complex. This preparation can prepare thefilm in-situ on a keratin substance such as skin.

However, it may be difficult to prepare the above film by the sprayingprocess disclosed in JP-A-2015-107939 without careful control, becauseit may not be easy to control the amounts of the first and secondsolutions to be sprayed. In particular, the preparation of a relativelythick film by using the spraying process disclosed in JP-A-2015-107939may be difficult.

One option to easily make a film made from a polyion complex may be touse a polyion complex in the form of particles. For example,JP-A-2005-36190 discloses a dispersion including polyion complexparticles which has been formed by an anionic polymer and a cationicpolymer.

DISCLOSURE OF INVENTION

However, it has been discovered that a dispersion including polyioncomplex particles is not always stable. If the dispersion is unstable,the polyion complex particles tend to precipitate.

Thus, a first objective of the present invention is to provide a stablecomposition, in particular a stable composition in the form of anemulsion, which includes polyion complex particles.

The above objective of the present invention can be achieved by acomposition, preferably a cosmetic composition, and more preferably askin cosmetic composition comprising:

(a) at least one particle, comprising

-   -   at least one cationic polymer and at least one anionic polymer,    -   at least one cationic polymer and at least one amphoteric        polymer,    -   at least one anionic polymer and at least one amphoteric        polymer, or    -   at least one amphoteric polymer,    -   and    -   at least one non-polymeric acid having two or more pKa values or        salt(s) thereof or    -   at least one non-polymeric base having two or more pKb values or        salt(s) thereof;

(b) at least one oil; and

(c) water.

A plurality of the (a) particles may be present at the interface betweenthe (b) oil and the (c) water, or may form a capsule having a hollow,and the (b) oil is present in the hollow.

The cationic polymer may have at least one positively chargeable and/orpositively charged moiety selected from the group consisting of aprimary, secondary or tertiary amino group, a quaternary ammonium group,a guanidine group, a biguanide group, an imidazole group, an iminogroup, and a pyridyl group.

The cationic polymer may be selected from the group consisting ofcyclopolymers of alkyldiallylamine and cyclopolymers ofdialkyldiallylammonium such as (co)polydiallyldialkyl ammonium chloride,(co)polyamines such as (co)polylysines and chitosans, cationic(co)polyaminoacids such as collagen, and salts thereof.

The anionic polymer may have at least one negatively chargeable and/ornegatively charged moiety selected from the group consisting of asulfuric group, a sulfate group, a sulfonic group, a sulfonate group, aphosphoric group, a phosphate group, a phosphonic group, a phosphonategroup, a carboxylic group, and a carboxylate group.

The anionic polymer may be selected from the group consisting ofpolysaccharides such as alginic acid, hyaluronic acid, and cellulosepolymers, anionic (co)polyaminoacids such as (co)polyglutamic acids,(co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrenesulfonate, (co)poly(vinyl sulfate), dextran sulfate, chondroitinsulfate, (co)polymaleic acids, (co)polyfumaric acids, maleic acid(co)polymers, and salts thereof.

The amphoteric polymer may have at least one positively chargeableand/or positively charged moiety selected from the group consisting of aprimary, secondary or tertiary amino group, a quaternary ammonium group,a guanidine group, a biguanide group, an imidazole group, an iminogroup, and a pyridyl group, and at least one negatively chargeableand/or negatively charged moiety selected from the group consisting of asulfuric group, a sulfate group, a sulfonic group, a sulfonate group, aphosphoric group, a phosphate group, a phosphonic group, a phosphonategroup, a carboxylic group, and a carboxylate group.

The amphoteric polymer may be selected from the group consisting ofpolyquaternium-22, polyquaternium-39, polyquaternium-53,polyquaternium-64, polyquaternium-51, polyquaternium-61, and mixturesthereof.

The amount of the polymer(s), in the composition according to thepresent invention may be from 0.001 to 25% by weight, preferably from0.1 to 20% by weight, and more preferably from 0.3 to 15% by weight,relative to the total weight of the composition.

The amount of the non-polymeric acid having two or more pKa values orsalt(s) thereof or non-polymeric base having two or more pKb values orsalt(s) thereof in the composition according to the present inventionmay be from 0.0001 to 30% by weight, preferably from 0.01 to 20% byweight, and more preferably from 0.1 to 15% by weight, relative to thetotal weight of the composition.

The (a) particle may comprise (d) at least one hydrophobic amino acidother than the non-polymeric acid or base.

The pH of the composition according to the present invention may be from3 to 9, preferably from 3.5 to 8.5, and more preferably from 4 to 8.

The amount of the (a) particle in the composition according to thepresent invention may be from 0.001 to 60% by weight, preferably from0.1 to 50% by weight, and more preferably from 1 to 40% by weight,relative to the total weight of the composition.

It is preferable that the (b) oil be selected from polar oils.

The amount of the (b) oil(s) in the composition may be from 0.01 to 50%by weight, preferably from 0.1 to 40% by weight, and more preferablyfrom 1 to 35% by weight, relative to the total weight of thecomposition.

It is preferable that the composition according to the present inventionbe in the form of an emulsion, more preferably an O/W emulsion, and evenmore preferably an O/W emulsion comprising 0.1% by weight or less ofsurfactant(s), preferably 0.01% by weight or less of surfactant(s), andmore preferably no surfactant(s).

It is preferable that the composition according to the present inventioncomprise (e) at least one oil gelling agent.

A second objective of the present invention is to provide a processwhich can easily prepare a film made from polyion complex particleswherein the film comprises at least one oil.

The above objective of the present invention can be achieved by aprocess for preparing a film, preferably a cosmetic film, comprising:

applying onto a substrate, preferably a keratin substrate, and morepreferably skin, the composition according to the present invention; and

drying the composition.

A third objective of the present invention is to provide a film madefrom polyion complex particles wherein the film comprises at least oneoil.

The above objective of the present invention can be achieved by:

(1) A film, preferably a cosmetic film, prepared by a processcomprising:

-   -   applying onto a substrate, preferably a keratin substrate, and        more preferably skin,    -   the composition according to the present invention; and    -   drying the composition,

or

(2) A film, preferably a cosmetic film, comprising:

-   -   at least one cationic polymer and at least one anionic polymer,    -   at least one cationic polymer and at least one amphoteric        polymer,    -   at least one anionic polymer and at least one amphoteric        polymer, or    -   at least one amphoteric polymer;    -   at least one non-polymeric acid having two or more pKa values or        salt(s) thereof or    -   at least one non-polymeric base having two or more pKb values or        salt(s) thereof;    -   and    -   at least one oil.

The present invention also relates to a cosmetic process for a keratinsubstrate such as skin, comprising

applying to the keratin substrate the composition according to thepresent invention; and drying the composition to form a cosmetic film onthe keratin substrate.

The cosmetic film thus obtained can be resistant to water with a pH of 7or less, and can be removable with water with a pH of more than 7,preferably 8 or more, and more preferably 9 or more.

The present invention also relates to a use of the composition accordingto the present invention for the preparation of a cosmetic film on akeratin substrate such as skin, wherein the cosmetic film is resistantto water with a pH of 7 or less, and is removable with water with a pHof more than 7, preferably 8 or more, and more preferably 9 or more.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 shows encapsulation of oil globules by the PGP according toExample 1.

BEST MODE FOR CARRYING OUT THE INVENTION

After diligent research, the inventors have discovered that it ispossible to provide a stable composition such as a stable emulsion,which includes polyion complex particles and oil(s). Thus, thecomposition according to the present invention comprises:

(a) at least one particle, comprising

-   -   at least one cationic polymer and at least one anionic polymer,    -   at least one cationic polymer and at least one amphoteric        polymer,    -   at least one anionic polymer and at least one amphoteric        polymer, or    -   at least one amphoteric polymer,    -   and    -   at least one non-polymeric acid having two or more pKa values or        salt(s) thereof or    -   at least one non-polymeric base having two or more pKb values or        salt(s) thereof;

(b) at least one oil; and

(c) water.

It may be preferable that a plurality of the (a) particles are presentat the interface between the (b) oil and the (c) water, or a pluralityof the (a) particles form a capsule having a hollow, and the (b) oil ispresent in the hollow.

Further, the inventors have discovered that it is possible to provide aprocess which can easily prepare a film comprising polyion complexparticles and oil(s). Thus, the process according to the presentinvention is a process for preparing a film, preferably a cosmetic film,the process comprising

applying onto a substrate, preferably a keratin substrate, thecomposition according to the present invention; and

drying the composition.

Furthermore, the inventors have discovered that it is possible toprovide a film comprising polyion complex particles and oil(s). Thus,the film according to the present invention is

(1) A film, preferably a cosmetic film, prepared by a processcomprising:

-   -   applying onto a substrate, preferably a keratin substrate, and        more preferably skin,    -   the composition according to the present invention; and    -   drying the composition,

or

(2) A film, preferably a cosmetic film, comprising:

-   -   at least one cationic polymer and at least one anionic polymer,    -   at least one cationic polymer and at least one amphoteric        polymer,    -   at least one anionic polymer and at least one amphoteric        polymer, or    -   at least one amphoteric polymer;    -   at least one non-polymeric acid having two or more pKa values or        salt(s) thereof or    -   at least one non-polymeric base having two or more pKb values or        salt(s);    -   and    -   at least one oil.

The composition according to the present invention is stable for a longperiod of time, and can be used to easily prepare a film of a polyioncomplex wherein the film includes at least one oil by applying thecomposition onto a substrate, preferably a keratin substrate such asskin and hair, and more preferably skin, and drying the composition.

The polyion complex film according to the present invention can have avariety of cosmetic functions.

For example, the film according to the present invention itself may havecosmetic effects such as moisturizing due to the oil(s), as well asabsorbing or adsorbing malodor, changing the appearance of a keratinsubstrate such as skin, changing the feel to the touch of the keratinsubstrate, and/or protecting the keratin substrate from, for example,dirt or pollutants.

It is also possible to realize sustained release of the oil(s) from thefilm.

If the polyion complex film includes at least one cosmetic activeingredient other than the oil(s), the film can have cosmetic effectsprovided by the cosmetic active ingredient(s). For example, if thepolyion complex film includes at least one cosmetic active ingredientselected from UV filters, anti-aging agents, anti-sebum agents,deodorant agents, anti-perspirant agents, whitening agents and a mixturethereof, the film can filter UV rays, treat the aging of the skin,absorb sebum on the skin, control odors on the skin, control theperspiration on the skin, and/or whiten the skin.

The film according to the present invention may be transparent, andtherefore, may not be easy to perceive, even when the film is relativelythick.

Further, the film according to the present invention is water-resistant,and therefore, it can remain on a keratin substrate such as skin even ifthe surface of the keratin substrate is wet due to, for example sweatand rain.

Furthermore, the film according to the present invention can be easilyremoved from a keratin substrate such as skin under alkaline conditions.Therefore, the film according to the present invention is difficult toremove with water, while it can be easily removed with a soap which canprovide alkaline conditions.

Thus, if the film according to the present invention includes ahydrophilic or water-soluble UV filter, the film according to thepresent invention can show UV shielding effects which are resistant towater (water-proof) and can be long-lasting, but can be easily removedwith a soap which can provide alkaline conditions.

Hereinafter, the composition, process, film and the like according tothe present invention will be explained in a more detailed manner.

[Polyion Complex Particle]

The composition according to the present invention includes (a) at leastone particle which is a polyion complex particle. Two or more differenttypes of (a) particles may be used in combination. Thus, a single typeof (a) particle or a combination of different types of (a) particles maybe used.

The size of the polyion complex particle may be from 5 nm to 100 μm,preferably from 100 nm to 50 μm, more preferably from 200 nm to 30 μm,and even more preferably from 500 nm to 20 μm. A particle size less than1 μm can be measured by a dynamic light scattering method, and aparticle size more than 1 μm can be measured by an optical microscope.This particle size may be based on number average diameter.

The amount of the (a) particle(s) in the composition according to thepresent invention may be 0.001% by weight or more, preferably 0.1% byweight or more, and more preferably 1% by weight or more, relative tothe total weight of the composition.

The amount of the (a) particle(s) in the composition according to thepresent invention may be 60% by weight or less, preferably 50% by weightor less, and more preferably 40% by weight or less, relative to thetotal weight of the composition.

The amount of the (a) particle(s) in the composition according to thepresent invention may be from 0.001 to 60% by weight, preferably from0.1 to 50% by weight, and more preferably from 1 to 40% by weight,relative to the total weight of the composition.

A plurality of the (a) particles can be present at the interface betweenthe (b) oil and the (c) water. Thus, the (a) particles can form anemulsion. For example, if the (c) water constitutes a continuous phaseand the (b) oil constitutes dispersed phases, the (a) particles can forman O/W emulsion which may be similar to a so-called Pickering emulsion.

Alternatively, a plurality of the (a) particles can form a capsulehaving a hollow. The (b) oil can be present in the hollow. In otherwords, the (b) oil can be incorporated into the capsule. The wall of thecapsule may be composed of a continuous layer or film formed from the(a) particles. While not wishing to be bound by theory, it is believedthat the (a) particles can re-organize at the interface of the (b) oiland the (c) water to spontaneously form a capsule having a hollow toinclude the (b) oil. For example, a continuous phase constituted withthe (c) water and a dispersed phases constituted with the (b) oil in thecapsule can form an O/W emulsion which may also be similar to aso-called Pickering emulsion.

The above would mean that the (a) particle itself is amphiphilic andinsoluble in oil or water.

The (a) particle includes at least one polymer or a combination ofpolymers. Specifically, the (a) particle includes:

(1) at least one cationic polymer and at least one anionic polymer;

(2) at least one cationic polymer and at least one amphoteric polymer;

(3) at least one anionic polymer and at least one amphoteric polymer; or

(4) at least one amphoteric polymer.

There is no limit to the type of the cationic, anionic and amphotericpolymers. Two or more different types of cationic polymers may be usedin combination. Thus, a single type of cationic polymer or a combinationof different types of cationic polymers may be used. Two or moredifferent types of anionic polymers may be used in combination. Thus, asingle type of anionic polymer or a combination of different types ofanionic polymers may be used.

Two or more different types of amphoteric polymers may be used incombination. Thus, a single type of amphoteric polymer or a combinationof different types of amphoteric polymers may be used.

In the above (1), the ratio of the amount, for example chemicalequivalent, of the cationic polymer(s)/the anionic polymer(s) may be0.05-18, preferably 0.1-10, and more preferably 0.5-5.0. In particular,it may be preferable that the number of the cationic groups of thecationic polymer(s)/the number of anionic groups of the anionicpolymer(s) be 0.05-18, more preferably 0.1-10, and even more preferably0.5-5.0.

In the above (2), the ratio of the amount, for example chemicalequivalent, of the cationic polymer(s)/the amphoteric polymer(s) may be0.05-18, preferably 0.1-10, and more preferably 0.5-5.0. In particular,it may be preferable that the number of the cationic groups of thecationic polymer(s)/the number of cationic and anionic groups of theamphoteric polymer(s) be 0.05-18, more preferably 0.1-10, and even morepreferably 0.5-5.0.

In the above (3), the ratio of the amount, for example chemicalequivalent, of the anionic polymer(s)/the amphoteric polymer(s) may be0.05-18, preferably 0.1-10, and more preferably 0.5-5.0. In particular,it may be preferable that the number of the anionic groups of theanionic polymer(s)/the number of cationic and anionic groups of theamphoteric polymer(s) be 0.05-18, more preferably 0.1-10, and even morepreferably 0.5-5.0.

The total amount of the polymer(s) according to any one of the above (1)to (4) in the composition according to the present invention may be0.001% by weight or more, preferably 0.1% by weight or more, and morepreferably 1% by weight or more, relative to the total weight of thecomposition.

The total amount of the polymer(s) according to any one of the above (1)to (4) in the composition according to the present invention may be 25%by weight or less, preferably 20% by weight or less, and more preferably15% by weight or less, relative to the total weight of the composition.

The total amount of the polymer(s) according to any one of the above (1)to (4) in the composition according to the present invention may be from0.001 to 25% by weight, preferably from 0.1 to 20% by weight, and morepreferably from 1 to 15% by weight, relative to the total weight of thecomposition.

(Cationic Polymer)

A cationic polymer has a positive charge density. The charge density ofthe cationic polymer may be from 0.01 meq/g to 20 meq/g, preferably from0.05 to15 meq/g, and more preferably from 0.1 to 10 meq/g.

It may be preferable that the molecular weight of the cationic polymerbe 500 or more, preferably 1000 or more, more preferably 2000 or more,and even more preferably 5000 or more.

Unless otherwise defined in the descriptions, “molecular weight” means anumber average molecular weight.

The cationic polymer may have at least one positively chargeable and/orpositively charged moiety selected from the group consisting of aprimary, secondary or tertiary amino group, a quaternary ammonium group,a guanidine group, a biguanide group, an imidazole group, an iminogroup, and a pyridyl group. The term (primary) “amino group” here meansa group of —NH₂.

The cationic polymer may be a homopolymer or a copolymer. The term“copolymer” is understood to mean both copolymers obtained from twokinds of monomers and those obtained from more than two kinds ofmonomers, such as terpolymers obtained from three kinds of monomers.

The cationic polymer may be selected from natural and synthetic cationicpolymers. Non-limiting examples of the cationic polymers are as follows.

(1) Homopolymers and copolymers derived from acrylic or methacrylicesters and amides and comprising at least one unit chosen from units ofthe following formulas:

wherein:

R₁ and R₂, which may be identical or different, are chosen from hydrogenand alkyl groups comprising from 1 to 6 carbon atoms, for instance,methyl and ethyl groups;

R₃, which may be identical or different, is chosen from hydrogen andCH₃;

the symbols A, which may be identical or different, are chosen fromlinear or branched alkyl groups comprising from 1 to 6 carbon atoms, forexample, from 2 to 3 carbon atoms and hydroxyalkyl groups comprisingfrom 1 to 4 carbon atoms;

R₄, R₅, and R₆, which may be identical or different, are chosen fromalkyl groups comprising from 1 to 18 carbon atoms and benzyl groups, andin at least one embodiment, alkyl groups comprising from 1 to 6 carbonatoms; and

X is an anion derived from an inorganic or organic acid, such asmethosulphate anions and halides, for instance chloride and bromide.

The copolymers of family (1) may also comprise at least one unit derivedfrom comonomers which may be chosen from acrylamides, methacrylamides,diacetone acrylamides, acrylamides and methacrylamides substituted onthe nitrogen atom with (C₁-C₄) lower alkyl groups, groups derived fromacrylic or methacrylic acids and esters thereof, vinyllactams such asvinylpyrrolidone and vinylcaprolactam, and vinyl esters.

Examples of copolymers of family (1) include, but are not limited to:

copolymers of acrylamide and of dimethylaminoethyl methacrylatequaternized with dimethyl sulphate or with a dimethyl halide,

copolymers of acrylamide and of methacryloyloxyethyltrimethylammoniumchloride described, for example, in European Patent Application No. 0080 976,

copolymers of acrylamide and of methacryloyloxyethyltrimethylammoniummethosulphate, quaternized or nonquaternizedvinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers,described, for example, in French Patent Nos. 2 077 143 and 2 393 573,dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidoneterpolymers, vinylpyrrolidone/methacrylamidopropyldimethylaminecopolymers, quaternizedvinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers, andcrosslinked methacryloyloxy(C₁-C₄)alkyltri(C₁-C₄)alkylammonium saltpolymers such as the polymers obtained by homopolymerization ofdimethylaminoethyl methacrylate quaternized with methyl chloride, or bycopolymerization of acrylamide with dimethylaminoethyl methacrylatequaternized with methyl chloride, the homopolymerization orcopolymerization being followed by crosslinking with a compoundcontaining an olefinic unsaturation, for example,methylenebisacrylamide.

(2) Cationic cellulose derivatives such as cellulose ether derivativescomprising quaternary ammonium groups described, for example, in FrenchPatent No. 1 492 597, such as the polymers sold under the names “JR” (JR400, JR 125, JR 30M) or “LR” (LR 400, LR 30M) by the company UnionCarbide Corporation. These polymers are also defined in the CTFAdictionary as quaternary ammoniums of hydroxyethylcellulose that havereacted with an epoxide substituted with a trimethylammonium group.

(3) Cationic cellulose derivatives such as cellulose copolymers andcellulose derivatives grafted with a water-soluble monomer of quaternaryammonium, and described, for example, in U.S. Pat. No. 4,131,576, suchas hydroxyalkylcelluloses, for instance, hydroxymethyl-, hydroxyethyl-,and hydroxypropylcelluloses grafted, for example, with a salt chosenfrom methacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium, and dimethyldiallylammoniumsalts.

Commercial products corresponding to these polymers include, forexample, the products sold under the name “Celquat® L 200” and “Celquat®H 100” by the company National Starch.

(4) Non-cellulose-based cationic polysaccharides described in U.S. Pat.Nos. 3,589,578 and 4,031,307, such as guar gums comprising cationictrialkylammonium groups, cationic hyaluronic acid, and dextranhydroxypropyl trimonium chloride. Guar gums modified with a salt, forexample the chloride, of 2,3-epoxypropyltrimethylammonium (guarhydroxypropyltrimonium chloride) may also be used.

Such products are sold, for instance, under the trade names JAGUAR® C13S, JAGUAR® C15, JAGUAR® C17, and JAGUAR® C162 by the company MEYHALL.

(5) Polymers comprising piperazinyl units and divalent alkylene orhydroxyalkylene groups comprising straight or branched chains,optionally interrupted with at least one entity chosen from oxygen,sulphur, nitrogen, aromatic rings, and heterocyclic rings, and also theoxidation and/or quaternization products of these polymers. Suchpolymers are described, for example, in French Patent Nos. 2.162 025 and2 280 361.

(6) Water-soluble polyamino amides prepared, for example, bypolycondensation of an acidic compound with a polyamine; these polyaminoamides possibly being crosslinked with an entity chosen fromepihalohydrins; diepoxides; dianhydrides; unsaturated dianhydrides;bisunsaturated derivatives; bishalohydrins; bisazetidiniums;bishaloacyidiamines; bisalkyl halides; oligomers resulting from thereaction of a difunctional compound which is reactive with an entitychosen from bishalohydrins, bisazetidiniums, bishaloacyldiamines,bisalkyl halides, epihalohydrins, diepoxides, and bisunsaturatedderivatives; the crosslinking agent being used in an amount ranging from0.025 to 0.35 mol per amine group of the polyamino amide; thesepolyamino amides optionally being alkylated or, if they comprise atleast one tertiary amine function, they may be quaternized. Suchpolymers are described, for example, in French Patent Nos. 2 252 840 and2 368 508.

(7) Polyamino amide derivatives resulting from the condensation ofpolyalkylene polyamines with polycarboxylic acids, followed byalkylation with difunctional agents, for example, adipicacid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which thealkyl group comprises from 1 to 4 carbon atoms, such as methyl, ethyl,and propyl groups, and the alkylene group comprises from 1 to 4 carbonatoms, such as an ethylene group. Such polymers are described, forinstance, in French Patent No. 1 583 363. In at least one embodiment,these derivatives may be chosen from adipicacid/dimethylaminohydroxypropyldiethylenetriamine polymers.

(8) Polymers obtained by reaction of a polyalkylene polyamine comprisingtwo primary amine groups and at least one secondary amine group, with adicarboxylic acid chosen from diglycolic acid and saturated aliphaticdicarboxylic acids comprising from 3 to 8 carbon atoms. The molar ratioof the polyalkylene polyamine to the dicarboxylic acid may range from0.8:1 to 1.4:1; the polyamino amide resulting therefrom being reactedwith epichlorohydrin in a molar ratio of epichlorohydrin relative to thesecondary amine group of the polyamino amide ranging from 0.5:1 to1.8:1. Such polymers are described, for example, in U.S. Pat. Nos.3,227,615 and 2,961,347.

(9) Cyclopolymers of alkyldiallylamine and cyclopolymers ofdialkyldiallyl-ammonium, such as homopolymers and copolymers comprising,as the main constituent of the chain, at least one unit chosen fromunits of formulas (Ia) and (Ib):

wherein:

k and t, which may be identical or different, are equal to 0 or 1, thesum k+t being equal to 1; R₁₂ is chosen from hydrogen and methyl groups;

R₁₀ and R₁₁, which may be identical or different, are chosen from alkylgroups comprising from 1 to 6 carbon atoms, hydroxyalkyl groups in whichthe alkyl group comprises, for example, from 1 to 5 carbon atoms, andlower (C₁-C₄)amidoalkyl groups, or R₁₀ and R₁₁ may form, together withthe nitrogen atom to which they are attached, heterocyclic groups suchas piperidinyl and morpholinyl; and

Y¹ is an anion such as bromide, chloride, acetate, borate, citrate,tartrate, bisulphate, bisulphite, sulphate, and phosphate. Thesepolymers are described, for example, in French Patent No. 2 080 759 andin its Certificate of Addition 2 190 406.

In one embodiment, R₁₀ and R₁₁, which may be identical or different, arechosen from alkyl groups comprising from 1 to 4 carbon atoms.

Examples of such polymers include, but are not limited to,(co)polydiallyldialkyl ammonium chloride such as thedimethyidiallylammonium chloride homopolymer sold under the name“MERQUAT® 100” by the company CALGON (and its homologues of lowweight-average molecular mass) and the copolymers ofdiallyldimethylammonium chloride and of acrylamide sold under the name“MERQUAT® 550”.

Quaternary diammonium polymers comprising at least one repeating unit offormula (II):

wherein:

R₁₃, R₁₄, R₁₅, and R₁₆, which may be identical or different, are chosenfrom aliphatic, alicyclic, and arylaliphatic groups comprising from 1 to20 carbon atoms and lower hydroxyalkyl aliphatic groups, oralternatively R₁₃, R₁₄, R₁₅, and R₁₆ may form, together or separately,with the nitrogen atoms to which they are attached, heterocyclesoptionally comprising a second heteroatom other than nitrogen, oralternatively R₁₃, R₁₄, R₁₅, and R₁₆, which may be identical ordifferent, are chosen from linear or branched C₁-C₆ alkyl groupssubstituted with at least one group chosen from nitrile groups, estergroups, acyl groups, amide groups, —CO—O—R₁₇-E groups, and —CO—NH—R₁₇-Egroups, wherein R₁₇ is an alkylene group and E is a quaternary ammoniumgroup;

A₁ and B₁, which may be identical or different, are chosen frompolymethylene groups comprising from 2 to 20 carbon atoms, which may belinear or branched, saturated or unsaturated, and which may comprise,linked or intercalated in the main chain, at least one entity chosenfrom aromatic rings, oxygen, sulphur, sulphoxide groups, sulphonegroups, disulphide groups, amino groups, alkylamino groups, hydroxylgroups, quaternary ammonium groups, ureido groups, amide groups, andester groups, and

X⁻ is an anion derived from an inorganic or organic acid;

A₁, R₁₃, and R₁₅ may form, together with the two nitrogen atoms to whichthey are attached, a piperazine ring;

if A₁ is chosen from linear or branched, saturated or unsaturatedalkylene or hydroxyalkylene groups, B₁ may be chosen from:

—(CH₂)_(n)—CO-E′-OC—(CH₂)_(n)—

wherein E¹ is chosen from:

a) glycol residues of formula —O—Z—O—, wherein Z is chosen from linearor branched hydrocarbon-based groups and groups of the followingformulas:

—(CH₂—CH₂—O)_(x)—CH₂—CH₂—

—[CH₂—CH(CH₃)—O]_(y)—CH₂—CH(CH₃)—

wherein x and y, which may be identical or different, are chosen fromintegers ranging from 1 to 4, which represent a defined and uniquedegree of polymerization, and numbers ranging from 1 to 4, whichrepresent an average degree of polymerization;

b) bis-secondary diamine residue such as piperazine derivatives;

c) bis-primary diamine residues of formula —NH—Y—NH—, wherein Y ischosen from linear or branched hydrocarbon-based groups and the divalentgroup —CH₂—CH₂—S—S—CH₂—CH₂—; and

d) ureylene groups of formula —NH—CO—NH—.

In at least one embodiment, X⁻ is an anion such as chloride or bromide.

Polymers of this type are described, for example, in French Patent Nos.2 320 330; 2 270 846; 2 316 271; 2 336 434; and 2 413 907 and U.S. Pat.Nos. 2,273,780; 2,375,853; 2,388,614; 2,454,547; 3,206,462; 2,261,002;2,271,378; 3,874,870; 4,001,432; 3,929,990; 3,966,904; 4,005,193;4,025,617; 4,025,627; 4,025,653; 4,026,945; and 4,027,020.

Non-limiting examples of such polymers include those comprising at leastone repeating unit of formula (III):

wherein R₁₃, R₁₄, R₁₅, and R₁₆, which may be identical or different, arechosen from alkyl and hydroxyalkyl groups comprising from 1 to 4 carbonatoms, n and p, which may be identical or different, are integersranging from 2 to 20, and X⁻ is an anion derived from an inorganic ororganic acid.

(11) Polyquaternary ammonium polymers comprising units of formula (IV):

-   -   wherein:

R₁₈, R₁₉, R₂₀, and R₂₁, which may be identical or different, are chosenfrom hydrogen, methyl groups, ethyl groups, propyl groups,β-hydroxyethyl groups, β-hydroxypropyl groups, —CH₂CH₂(OCH₂CH₂)_(p)OHgroups, wherein p is chosen from integers ranging from 0 to 6, with theproviso that R₁₈, R₁₉, R₂₀, and R₂₁ are not simultaneously hydrogen,

r and s, which may be identical or different, are chosen from integersranging from 1 to 6,

q is chosen from integers ranging from 0 to 34,

X⁻ is an anion such as a halide, and

A is chosen from radicals of dihalides and —CH₂—CH₂—O—CH₂—CH₂—.

Such compounds are described, for instance, in European PatentApplication No. 0 122 324.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole.

Other examples of suitable cationic polymers include, but are notlimited to, cationic proteins and cationic protein hydrolysates,polyalkyleneimines, such as polyethyleneimines, polymers comprisingunits chosen from vinylpyridine and vinylpyridinium units, condensatesof polyamines and of epichlorohydrin, quaternary polyureylenes, andchitin derivatives.

According to one embodiment of the present invention, the at least onecationic polymer is chosen from cellulose ether derivatives comprisingquaternary ammonium groups, such as the products sold under the name “JR400” by the company UNION CARBIDE CORPORATION, cationic cyclopolymers,for instance, the homo-polymers and copolymers ofdimethyldiallylammonium chloride sold under the names MERQUAT® 100,MERQUAT® 550, and MERQUAT® S by the company CALGON, guar gums modifiedwith a 2,3-epoxypropyltrimethylammonium salt, and quaternary polymers ofvinylpyrrolidone and of vinylimidazole.

(13) Polyamines

As the cationic polymer, it is also possible to use (co)polyamines,which may be homopolymers or copolymers, with a plurality of aminogroups. The amino group may be a primary, secondary, tertiary orquaternary amino group. The amino group may be present in a polymerbackbone or a pendent group, if present, of the (co)polyamines.

As example of the (co)polyamines, mention may be made of chitosan,(co)polyallylamines, (co)polyvinylamines, (co)polyanilines,(co)polyvinylimidazoles, (co)polydimethylaminoethylenemethacrylates,(co)polyvinylpyridines such as (co)poly-1-methyl-2-vinylpyridines,(co)polyimines such as (co) polyethyleneimines, (co)polypyridines suchas (co)poly(quaternary pyridines), (co)polybiguanides such as(co)polyaminopropyl biguanides, (co)polylysines, (co)polyornithines,(co)polyarginines, (co)polyhistidines, aminodextrans, aminocelluloses,amino(co)polyvinylacetals, and salts thereof.

As the (co)polyamines, it is preferable to use (co)polylysines.Polylysine is well known. Polylysine can be a natural homopolymer ofL-lysine that can be produced by bacterial fermentation. For example,polylysine can be ε-Poly-L-lysine, typically used as a naturalpreservative in food products. Polylysine is a polyelectrolyte which issoluble in polar solvents such as water, propylene glycol and glycerol.Polylysine is commercially available in various forms, such as polyD-lysine and poly L-lysine. Polylysine can be in salt and/or solutionform.

(14) Cationic Polyaminoacids

As the cationic polymer, it may be possible use cationic polyaminoacids,which may be cationic homopolymers or copolymers, with a plurality ofamino groups and carboxyl groups. The amino group may be a primary,secondary, tertiary or quaternary amino group. The amino group may bepresent in a polymer backbone or a pendent group, if present, of thecationic polyaminoacids. The carboxyl group may be present in a pendentgroup, if present, of the cationic polyaminoacids.

As examples of the cationic polyaminoacids, mention may be made ofcationized collagen, cationized gelatin, steardimoium hydroxyprolylhydrolyzed wheat protein, cocodimonium hydroxypropyl hydrolyzed wheatprotein, hydroxypropyltrimonium hydrolyzed conchiolin protein,steardimonium hydroxypropyl hydrolyzed soy protein,hydroxypropyltrimonium hydrolyzed soy protein, cocodimoniumhydroxypropyl hydrolyzed soy protein, and the like.

It may be preferable that the cationic polymer be selected from thegroup consisting of cyclopolymers of alkyldiallylamine and cyclopolymersof dialkyldiallylammonium such as (co)polydiallyldialkyl ammoniumchloride, (co)polyamines such as (co)polylysines, cationic(co)polyaminoacids such as cationized collagen, and salts thereof.

The amount of the cationic polymer(s) in the composition according tothe present invention may be 0.001% by weight or more, preferably 0.1%by weight or more, and more preferably 1% by weight or more, relative tothe total weight of the composition.

The amount of the cationic polymer(s) in the composition according tothe present invention may be 25% by weight or less, preferably 20% byweight or less, and more preferably 15% by weight or less, relative tothe total weight of the composition.

The amount of the cationic polymer(s) in the composition according tothe present invention may be from 0.001 to 25% by weight, preferablyfrom 0.1 to 20% by weight, and more preferably from 1 to 15% by weight,relative to the total weight of the composition.

(Anionic Polymer)

An anionic polymer has a positive charge density. The charge density ofthe anionic polymer may be from 0.1 meq/g to 20 meq/g, preferably from 1to 15 meq/g, and more preferably from 4 to 10 meq/g if the anionicpolymer is a synthetic anionic polymer, and the average substitutiondegree of the anionic polymer may be from 0.1 to 3.0, preferably from0.2 to 2.7, and more preferably from 0.3 to 2.5 if the anionic polymeris a natural anionic polymer.

It may be preferable that the molecular weight of the anionic polymer be1,000 or more, preferably 10,000 or more, more preferably 50,000 ormore, and even more preferably 1,000,00 or more.

The anionic polymer may have at least one negatively chargeable and/ornegatively charged moiety selected from the group consisting of asulfuric group, a sulfate group, a sulfonic group, a sulfonate group, aphosphoric group, a phosphate group, a phosphonic group, a phosphonategroup, a carboxylic group, and a carboxylate group.

The anionic polymer may be a homopolymer or a copolymer. The term“copolymer” is understood to mean both copolymers obtained from twokinds of monomers and those obtained from more than two kinds ofmonomers, such as terpolymers obtained from three kinds of monomers.

The anionic polymer may be selected from natural and synthetic anionicpolymers.

The anionic polymer may comprise at least one hydrophobic chain.

The anionic polymer which may comprise at least one hydrophobic chainmay be obtained by copolymerization of a monomer (a) chosen fromcarboxylic acids comprising α,β-ethylenic unsaturation (monomer a′) and2-acrylamido-2-methylpropanesulphonic acid (monomer a″) with anon-surface-active monomer (b) comprising an ethylenic unsaturationother than (a) and/or a monomer (c) comprising an ethylenic unsaturationresulting from the reaction of an acrylic monomer comprising anα,β-monoethylenic unsaturation or of an isocyanate monomer comprising amonoethylenic unsaturation with a monohydric nonionic amphiphiliccomponent or with a primary or secondary fatty amine.

Thus, the anionic polymer with at least one hydrophobic chain may beobtained by two synthetic routes:

-   -   either by copolymerization of the monomers (a′) and (c), or        (a′), (b) and (c), or (a″) and (c), or (a″), (b) and (c),    -   or by modification (and in particular esterification or        amidation) of a copolymer formed from the monomers (a′) or from        the monomers (a′) and (b), or (a″) and (b), by a monohydric        nonionic amphiphilic compound or a primary or secondary fatty        amine.

Mention may in particular be made, as2-acrylamido-2-methylpropanesulphonic acid copolymers, of thosedisclosed in the article “Micelle formation of random copolymers ofsodium 2-(acrylamido)-2-methylpropanesulfonate and nonionic surfactantmacromonomer in water as studied by fluorescence and dynamic lightscattering—Macromolecules, 2000, Vol. 33, No. 10-3694-3704” and inapplications EP-A-0 750 899 and EP-A-1 069 172.

The carboxylic acid comprising an α,β-monoethylenic unsaturationconstituting the monomer (a′) can be chosen from numerous acids and inparticular from acrylic acid, methacrylic acid, crotonic acid, itaconicacid and maleic acid. It is preferably acrylic or methacrylic acid.

The copolymer can comprise a monomer (b) comprising a monoethylenicunsaturation which does not have a surfactant property. The preferredmonomers are those which give water-insoluble polymers when they arehomopolymerized. They can be chosen, for example, from C₁-C₄ alkylacrylates and methacrylates, such as methyl acrylate, ethyl acrylate,butyl acrylate or the corresponding methacrylates. The more particularlypreferred monomers are methyl acrylate and ethyl acrylate. The othermonomers which can be used are, for example, styrene, vinyltoluene,vinyl acetate, acrylonitrile and vinylidene chloride. Unreactivemonomers are preferred, these monomers being those in which the singleethylenic group is the only group which is reactive under thepolymerization conditions. However, monomers which comprise groups whichreact under the effect of heat, such as hydroxyethyl acrylate, canoptionally be used.

The monomer (c) is obtained by reaction of an acrylic monomer comprisingα,β-monoethylenic unsaturation, such as (a), or of an isocyanate monomercomprising monoethylenic unsaturation with a monohydric nonionicamphiphilic compound or a primary or secondary fatty amine.

The monohydric nonionic amphiphilic compounds or the primary orsecondary fatty amines used to produce the nonionic monomer (c) are wellknown. The monohydric nonionic amphiphilic compounds are generallyalkoxylated hydrophobic compounds comprising an alkylene oxide formingthe hydrophilic part of the molecule. The hydrophobic compounds aregenerally composed of an aliphatic alcohol or an alkylphenol, in whichcompounds a carbonaceous chain comprising at least six carbon atomsconstitutes the hydrophobic part of the amphiphilic compound.

The preferred monohydric nonionic amphiphilic compounds are compoundshaving the following formula (V):

R—(OCH₂CHR′)_(m)—(OCH₂CH₂)_(n)—OH  (V)

in which R is chosen from alkyl or alkylene groups comprising from 6 to30 carbon atoms and alkylaryl groups having alkyl radicals comprisingfrom 8 to 30 carbon atoms, R′ is chosen from alkyl groups comprisingfrom 1 to 4 carbon atoms, n is a mean number ranging from approximately1 to 150 and m is a mean number ranging from approximately 0 to 50,provided that n is at least as great as m.

Preferably, in the compounds of formula (V), the R group is chosen fromalkyl groups comprising from 12 to 26 carbon atoms and alkylphenylgroups in which the alkyl group is C₈-C₁₃; the R′ group is the methylgroup; m=0 and n=1 to 25.

The preferred primary and secondary fatty amines are composed of one ortwo alkyl chains comprising from 6 to 30 carbon atoms.

The monomer used to form the nonionic urethane monomer (c) can be chosenfrom highly varied compounds. Use may be made of any compound comprisinga copolymerizable unsaturation, such as an acrylic, methacrylic orallylic unsaturation. The monomer (c) can be obtained in particular froman isocyanate comprising a monoethylenic unsaturation, such as, inparticular, α,α-dimethyl-m-isopropenylbenzyl isocyanate.

The monomer (c) can be chosen in particular from acrylates,methacrylates or itaconates of oxyethylenated (1 to 50 EO) C₆-C₃₀ fattyalcohol, such as steareth-20 methacrylate, oxyethylenated (25 EO)behenyl methacrylate, oxyethylenated (20 EO) monocetyl itaconate,oxyethylenated (20 EO) monostearyl itaconate or the acrylate modified bypolyoxyethylenated (25 EO) C₁₂-C₂₄ alcohols and fromdimethyl-m-isopropenylbenzyl isocyanates of oxyethylenated (1 to 50 EO)C₆-C₃₀ fatty alcohol, such as, in particular, thedimethyl-m-isopropenylbenzyl isocyanate of oxyethylenated behenylalcohol.

According to a specific embodiment of the present invention, the anionicpolymer is chosen from acrylic terpolymers obtained from (a) acarboxylic acid comprising an α,β-ethylenic unsaturation, (b) anon-surface-active monomer comprising an ethylenic unsaturation otherthan (a), and (c) a nonionic urethane monomer which is the reactionproduct of a monohydric nonionic amphiphilic compound with an isocyanatecomprising a monoethylenic unsaturation.

Mention may in particular be made, as anionic polymers comprising atleast one hydrophobic chain, of the acrylic acid/ethyl acrylate/alkylacrylate terpolymer, such as the product as a 30% aqueous dispersionsold under the name Acusol 823 by Rohm & Haas; the acrylates/steareth-20methacrylate copolymer, such as the product sold under the name Aculyn22 by Rohm & Haas; the (meth)acrylic acid/ethyl acrylate/oxyethylenated(25 EO) behenyl methacrylate terpolymer, such as the product as anaqueous emulsion sold under the name Aculyn 28 by Rohm & Haas; theacrylic acid/oxyethylenated (20 EO) monocetyl itaconate copolymer, suchas the product as a 30% aqueous dispersion sold under the name Structure3001 by National Starch; the acrylic acid/oxyethylenated (20 EO)monostearyl itaconate copolymer, such as the product as a 30% aqueousdispersion sold under the name Structure 2001 by National Starch; theacrylates/acrylate modified by polyoxyethylenated (25 EO) C₁₂-C₂₄alcohol copolymer, such as the 30-32% copolymer latex sold under thename Synthalen W2000 by 3V SA; or the methacrylic acid/methylacrylate/dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylatedbehenyl alcohol terpolymer, such as the product as a 24% aqueousdispersion and comprising 40 ethylene oxide groups disclosed in thedocument EP-A-0 173 109.

The anionic polymers may also be Polyester-5, such as the product soldunder the name of Eastman AQ™ 55S Polymer by EASTMAN CHEMICAL having achemical formula below.

A: dicarboxylic acid moiety

G: glycol moiety

SO₃ ⁻Na⁺: sodium sulfo group

OH: hydroxyl group

It may be preferable that the anionic polymer be selected from the groupconsisting of polysaccharides such as alginic acid, hyaluronic acid, andcellulose polymers (e.g., carboxymethylcellulose), anionic(co)polyaminoacids such as (co)polyglutamic acids, (co)poly(meth)acrylicacids, (co)polyamic acids, (co)polystyrene sulfonate, (co)poly(vinylsulfate), dextran sulfate, chondroitin sulfate, (co)polymaleic acids,(co)polyfumaric acids, maleic acid (co)polymers, and salts thereof.

The maleic acid copolymer may comprise one or more maleic acidcomonomers, and one or more comonomers chosen from vinyl acetate, vinylalcohol, vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms,and styrene.

Thus, the “maleic acid copolymer” is understood to mean any polymerobtained by copolymerization of one or more maleic acid comonomers andof one or more comonomers chosen from vinyl acetate, vinyl alcohol,vinylpyrrolidone, olefins comprising from 2 to 20 carbon atoms, such asoctadecene, ethylene, isobutylene, diisobutylene or isooctylene, andstyrene, the maleic acid comonomers optionally being partially orcompletely hydrolysed.

Use will preferably be made of hydrophilic polymers, that is to saypolymers having a solubility of water of greater than or equal to 2 g/l.

In an advantageous aspect of the present invention, the maleic acidcopolymer may have a molar fraction of maleic acid units of between 0.1and 1, more preferably between 0.4 and 0.9.

The weight-average molar mass of the maleic acid copolymer may bebetween 1,000 and 500,000, and preferably between 1,000 and 50,000.

It is preferable that the maleic acid copolymer be a styrene/maleic acidcopolymer, and more preferably sodium styrene/maleic acid copolymer.

Use will preferably be made of a copolymer of styrene and of maleic acidin a 50/50 ratio.

Use may be made, for example, of the styrene/maleic acid (50/50)copolymer, in the form of an ammonium salt at 30% in water, sold underthe reference SMA1000H® by Cray Valley or the styrene/maleic acid(50/50) copolymer, in the form of a sodium salt at 40% in water, soldunder the reference SMA1000HNa® by Cray Valley.

The use of the styrene/maleic acid copolymer such as sodiumstyrene/maleic acid copolymer can improve the wettability of a filmprepared by the composition according to the present invention.

The amount of the anionic polymer(s) in the composition according to thepresent invention may be 0.001% by weight or more, preferably 0.1% byweight or more, and more preferably 1% by weight or more, relative tothe total weight of the composition.

The amount of the anionic polymer(s) in the composition according to thepresent invention may be 25% by weight or less, preferably 20% by weightor less, and more preferably 15% by weight or less, relative to thetotal weight of the composition.

The amount of the anionic polymer(s) in the composition according to thepresent invention may be from 0.001 to 25% by weight, preferably from0.1 to 20% by weight, and more preferably from 1 to 15% by weight,relative to the total weight of the composition.

(Amphoteric Polymer)

An amphoteric polymer has both a positive charge density and a negativecharge density.

The positive charge density of the amphoteric polymer may be from 0.01meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g, and more preferablyfrom 0.1 to 10 meq/g.

The negative charge density of the amphoteric polymer may be from 0.01meq/g to 20 meq/g, preferably from 0.05 to 15 meq/g, and more preferablyfrom 0.1 to 10 meq/g.

It may be preferable that the molecular weight of the amphoteric polymerbe 500 or more, preferably 1000 or more, more preferably 2000 or more,and even more preferably 5000 or more.

Unless otherwise defined in the descriptions, “molecular weight” means anumber average molecular weight.

The amphoteric polymer may have

at least one positively chargeable and/or positively charged moietyselected from the group consisting of a primary, secondary or tertiaryamino group, a quaternary ammonium group, a guanidine group, a biguanidegroup, an imidazole group, an imino group, and a pyridyl group, and

at least one negatively chargeable and/or negatively charged moietyselected from the group consisting of a sulfuric group, a sulfate group,a sulfonic group, a sulfonate group, a phosphoric group, a phosphategroup, a phosphonic group, a phosphonate group, a carboxylic group, anda carboxylate group.

The amphoteric polymer may be a homopolymer or a copolymer. The term“copolymer” is understood to mean both copolymers obtained from twokinds of monomers and those obtained from more than two kinds ofmonomers, such as terpolymers obtained from three kinds of monomers.

The amphoteric polymers which can be used in accordance with the presentinvention may be chosen from the polymers containing K and M unitsdistributed randomly in the polymer chain where K denotes a unit whichis derived from a monomer containing at least one basic nitrogen atomand M denotes a unit which is derived from an acidic monomer containingone or more carboxylic or sulphonic groups or alternatively K and M maydenote groups which are derived from zwitterionic monomers ofcarboxybetaines or of sulphobetaines. K and M may also denote a cationicpolymer chain containing primary, secondary, tertiary or quaternaryamine groups, in which at least one of the amine groups carries acarboxylic or sulphonic group linked through a hydrocarbon radical oralternatively K and M form part of a chain of a polymer with anα,β-dicarboxylic ethylene unit in which one of the carboxylic groups hasbeen caused to react with a polyamine containing one or more primary orsecondary amine groups.

The amphoteric polymers corresponding to the definition given abovewhich are more particularly preferred are chosen from the followingpolymers:

(1) The polymers resulting from the copolymerization of a monomerderived from a vinyl compound carrying a carboxylic group such as moreparticularly acrylic acid, methacrylic acid, maleic acid,alpha-chloroacrylic acid, and from a basic monomer derived from asubstituted vinyl compound containing at least one basic atom such asmore particularly dialkylaminoalkyl methacrylate and acrylate,dialkylaminoalkylmethacrylamide and acrylamide. Such compounds aredescribed in U.S. Pat. No. 3,836,537. There may also be mentioned thesodium acrylate/acrylamidopropyltrimethylammonium chloride copolymersold under the name POLYQUART KE 3033 by the company HENKEL. The vinylcompound may also be a dialkyldiallylammonium salt such asdimethyldiallylammonium chloride. The copolymers of acrylic acid and ofthe latter monomer are provided under the names MERQUAT 280, MERQUAT295, MERQUAT 2003 PR, MERQUAT 3330 PR, and MERQUAT PLUS 3330 by thecompany Lubrizol.

(2) The polymers containing units which are derived from:

a) at least one monomer chosen from acrylamides or methacrylamidessubstituted on the nitrogen by an alkyl radical,

b) at least one acidic comonomer containing one or more reactivecarboxylic groups, and

c) at least one basic comonomer such as esters with primary, secondary,tertiary and quaternary amine substituents of acrylic and methacrylicacids and the product of quaternization of dimethylaminoethylmethacrylate with dimethyl or diethyl sulphate.

The N-substituted acrylamides or methacrylamides most particularlypreferred according to the invention are groups whose alkyl radicalscontain from 2 to 12 carbon atoms and more particularlyN-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide,N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as thecorresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic,methacrylic, crotonic, itaconic, maleic and fumaric acids as well as thealkyl monoesters having 1 to 4 carbon atoms of maleic or fumaricanhydrides or acids.

The basic comonomers preferred are methacrylates of aminoethyl,butylaminoethyl, N,N′-dimethylaminoethyl, N-tert-butylaminoethyl.

Particularly used are the copolymers whose CTFA name (4th ed. 1991) isOctylacrylamide/acrylates/butylaminoethylmethacrylate copolymer such asthe products sold under the name AMPHOMER or LOVOCRYL 47 by the companyNATIONAL STARCH.

(3) The partially or completely alkylated and crosslinkedpolyaminoamides derived from polyaminoamides of the following generalformula:

—[—CO—R₄—CO—Z—]—

in which R₄ represents a divalent radical derived from a saturateddicarboxylic acid, a mono- or dicarboxylic aliphatic acid with ethylenicdouble bond, an ester of a lower alkanol having 1 to 6 carbon atoms ofthese acids or a radical which is derived from the addition of any oneof the said acids with a bis-primary or bis-secondary amine, and Zdenotes a radical of a bis-primary, mono- or bis-secondarypolyalkylene-polyamine and preferably represents: a) in the proportionsof 60 to 100 mol %, the radical

—NH—[(CH₂)_(x)—NH—]_(p)—

where x=2 and p=2 or 3, or alternatively x=3 and p=2, this radical beingderived from the diethylenetriamine, triethylenetetraamine ordipropylenetriamine;

b) in the proportions of 0 to 40 mol %, the radical (IV) above, in whichx=2 and p=1 and which is derived from ethylenediamine, or the radicalwhich is derived from piperazine:

c) in the proportions of 0 to 20 mol %, the radical —NH—(CH₂)₆—NH— whichis derived from hexamethylenediamine, these polyamino amines beingcrosslinked by adding a bifunctional crosslinking agent chosen from theepihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives,by means of 0.025 to 0.35 mol of crosslinking agent per amine group ofthe polyamino amide and alkylated by the action of acrylic acid,chloroacetic acid or of an alkanesultone or of their salts.

The saturated carboxylic acids are preferably chosen from the acidshaving 6 to 10 carbon atoms such as adipic, 2,2,4-trimethyladipic and2,4,4-trimethyladipic acid, terephthalic acid, the acids with ethylenedouble bond such as for example acrylic, methacrylic and itaconic acids.

The alkanesultones used in the alkylation are preferably propane orbutanesultone, and the salts of the alkylating agents are preferably thesodium or potassium salts.

(4) The polymers containing zwitterionic units of formula:

in which R₅ denotes a polymerizable unsaturated group such as anacrylate, methacrylate, acrylamide or methacrylamide group, y and zrepresent an integer from 1 to 3, R₆ and R₇ represent a hydrogen atom,methyl, ethyl or propyl, R₈ and R₉ represent a hydrogen atom or an alkylradical such that the sum of the carbon atoms in R₈ and R₉ does notexceed 10.

The polymers comprising such units may also comprise units derived fromnonzwitterionic monomers such as dimethyl or diethylaminoethyl acrylateor methacrylate or alkyl acrylates or methacrylates, acrylamides ormethacrylamides or vinyl acetate.

By way of example, there may be mentioned the copolymer of butylmethacrylate/dimethylcarboxymethylammonioethyl methacrylate such as theproduct sold under the name DIAFORMER Z301 by the company SANDOZ.

(5) The polymers derived from chitosan containing monomeric unitscorresponding to the following formulae (VI), (VII), and (VIII):

the (VI) unit being present in proportions of from 0 to 30%, the (VII)unit in proportions of from 5 to 50% and the (VIII) unit in proportionsof from 30 to 90%, it being understood that in this (VIII) unit, R₁₀represents a radical of formula:

in which

if q=0, R₁₁, R₁₂ and R₁₃, which are identical or different, eachrepresent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue,a monoalkylamine residue or a dialkylamine residue optionallyinterrupted by one or more nitrogen atoms and/or optionally substitutedwith one or more amine, hydroxyl, carboxyl, alkylthio or sulphonicgroups, or an alkylthio residue whose alkyl group carries an aminoresidue, at least one of the R₁₁, R₁₂ and R₁₃ radicals being in thiscase a hydrogen atom;

or if q=1, R₁₁, R₁₂ and R₁₃ each represent a hydrogen atom, as well asthe salts formed by these compounds with bases or acids.

(6) The polymers derived from the N-carboxyalkylation of chitosan suchas N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under thename “EVALSAN” by the company JAN DEKKER.

(7) The polymers corresponding to the general formula (IX) such as thosedescribed for example in French Patent 1,400,366:

in which R₁₄ represents a hydrogen atom, a CH₃O, CH₃CH₂O or phenylradical, R₁₅ denotes hydrogen or a lower alkyl radical such as methyl orethyl, R₁₆ denotes hydrogen or a lower alkyl radical such as methyl orethyl, R₁₇ denotes a lower alkyl radical such as methyl or ethyl or aradical corresponding to the formula: —R₁₈—N(R₁₆)₂, R₁₈ representing agroup —CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)—, R₁₆ having the meaningsmentioned above, as well as the higher homologues of these radicals andcontaining up to 6 carbon atoms.

(8) Amphoteric polymers of the -D-X-D-X— type chosen from:

a) the polymers obtained by the action of chloroacetic acid or sodiumchloroacetate on the compounds containing at least one unit of formula:

-D-X-D-X-D-  (X)

where D denotes a radical

and X denotes the symbol E or E′, E or E′, which are identical ordifferent, denote a bivalent radical which is an alkylene radical with alinear or branched chain containing up to 7 carbon atoms in theprincipal chain which is unsubstituted or substituted with hydroxylgroups and which may contain, in addition, oxygen, nitrogen or sulphuratoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogenand sulphur atoms being present in the form of ether, thioether,sulphoxide, sulphone, sulphonium, alkylamine or alkenylamine groups, orhydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide,alcohol, ester and/or urethane groups.

b) The polymers of formula:

-D-X-D-X—  (XI)

where D denotes a radical

and X denotes the symbol E or E′ and, at least once, E′; E having themeaning indicated above and E′ is a bivalent radical which is analkylene radical with a linear or branched chain having up to 7 carbonatoms in the principal chain, which is unsubstituted or substituted withone or more hydroxyl radicals and containing one or more nitrogen atoms,the nitrogen atom being substituted with an alkyl chain optionallyinterrupted by an oxygen atom and necessarily containing one or morecarboxyl functional groups or one or more hydroxyl functional groups andbetainized by reaction with chloroacetic acid or sodium chloroacetate.

(9) The copolymers (C₁-C₅)alkyl vinyl ether/maleic anhydride partiallymodified by semiamidation with an N,N-dialkylaminoalkylamine such asN,N-dimethylaminopropylamine or by semiesterification with anN,N-dialkanolamine. These copolymers may also contain other vinylcomonomers such as vinylcaprolactam.

The amphoteric polymers particularly preferred according to theinvention are those of the family (1), particularly those containing asalt of dialkyldiallyl ammonium as a cationic monomer.

The amphoteric polymers may be chosen from polyquaternium-22,polyquaternium-39, polyquaternium-53, polyquaternium-64,polyquaternium-51, polyquaternium-61 and mixtures thereof.Polyquaternium-39 and polyquaternium-53, for example the product Merquat3330 PR and Merquat 2003 PR, sold by Lubrizol, are more preferable.

The amount of the amphoteric polymer(s) in the composition according tothe present invention may be 0.001% by weight or more, preferably 0.1%by weight or more, and more preferably 1% by weight or more, relative tothe total weight of the composition.

The amount of the amphoteric polymer(s) in the composition according tothe present invention may be 25% by weight or less, preferably 20% byweight or less, and more preferably 15% by weight or less, relative tothe total weight of the composition.

The amount of the amphoteric polymer(s) in the composition according tothe present invention may be from 0.001 to 25% by weight, preferablyfrom 0.1 to 20% by weight, and more preferably from 1 to 15% by weight,relative to the total weight of the composition.

[Oil]

The composition according to the present invention comprises (b) atleast one oil. If two or more (b) oils are used, they may be the same ordifferent.

Here, “oil” means a fatty compound or substance which is in the form ofa liquid or a paste (non-solid) at room temperature (25° C.) underatmospheric pressure (760 mmHg). As the oils, those generally used incosmetics can be used alone or in combination thereof. These oils may bevolatile or non-volatile.

The oil may be a non-polar oil such as a hydrocarbon oil, a siliconeoil, or the like; a polar oil such as a plant or animal oil and an esteroil or an ether oil; or a mixture thereof.

The oil may be selected from the group consisting of oils of plant oranimal origin, synthetic oils, silicone oils, hydrocarbon oils and fattyalcohols.

As examples of plant oils, mention may be made of, for example, linseedoil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil,avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil,sunflower oil, almond oil, rapeseed oil, sesame oil, soybean oil, peanutoil, and mixtures thereof.

As examples of animal oils, mention may be made of, for example,squalene and squalane.

As examples of synthetic oils, mention may be made of alkane oils suchas isododecane and isohexadecane, ester oils, ether oils, and artificialtriglycerides.

The ester oils are preferably liquid esters of saturated or unsaturated,linear or branched C₁-C₂₆ aliphatic monoacids or polyacids and ofsaturated or unsaturated, linear or branched C₁-C₂₆ aliphaticmonoalcohols or polyalcohols, the total number of carbon atoms of theesters being greater than or equal to 10.

Preferably, for the esters of monoalcohols, at least one from among thealcohol and the acid from which the esters of the present invention arederived is branched.

Among the monoesters of monoacids and of monoalcohols, mention may bemade of ethyl palmitate, ethyl hexyl palmitate, isopropyl palmitate,dicaprylyl carbonate, alkyl myristates such as isopropyl myristate orethyl myristate, isocetyl stearate, 2-ethylhexyl isononanoate, isononylisononanoate, isodecyl neopentanoate and isostearyl neopentanoate.

Esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of C₁-C₂₂alcohols, and esters of monocarboxylic, dicarboxylic or tricarboxylicacids and of non-sugar C₄-C₂₆ dihydroxy, trihydroxy, tetrahydroxy orpentahydroxy alcohols may also be used.

Mention may especially be made of: diethyl sebacate; isopropyl lauroylsarcosinate; diisopropyl sebacate; bis(2-ethylhexyl) sebacate;diisopropyl adipate; di-n-propyl adipate; dioctyl adipate;bis(2-ethylhexyl) adipate; diisostearyl adipate; bis(2-ethylhexyl)maleate; triisopropyl citrate; triisocetyl citrate; triisostearylcitrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecylcitrate; trioleyl citrate; neopentyl glycol diheptanoate; diethyleneglycol diisononanoate.

As ester oils, one can use sugar esters and diesters of C₆-C₃₀ andpreferably C₁₂-C₂₂ fatty acids. It is recalled that the term “sugar”means oxygen-bearing hydrocarbon-based compounds containing severalalcohol functions, with or without aldehyde or ketone functions, andwhich comprise at least 4 carbon atoms. These sugars may bemonosaccharides, oligosaccharides or polysaccharides.

Examples of suitable sugars that may be mentioned include sucrose (orsaccharose), glucose, galactose, ribose, fucose, maltose, fructose,mannose, arabinose, xylose and lactose, and derivatives thereof,especially alkyl derivatives, such as methyl derivatives, for instancemethylglucose.

The sugar esters of fatty acids may be chosen especially from the groupcomprising the esters or mixtures of esters of sugars describedpreviously and of linear or branched, saturated or unsaturated C₆-C₃₀and preferably C₁₂-C₂₂ fatty acids. If they are unsaturated, thesecompounds may have one to three conjugated or non-conjugatedcarbon-carbon double bonds.

The esters according to this variant may also be selected frommonoesters, diesters, triesters, tetraesters and polyesters, andmixtures thereof.

These esters may be, for example, oleates, laurates, palmitates,myristates, behenates, cocoates, stearates, linoleates, linolenates,caprates and arachidonates, or mixtures thereof such as, especially,oleopalmitate, oleostearate and palmitostearate mixed esters, as well aspentaerythrityl tetraethyl hexanoate.

More particularly, use is made of monoesters and diesters and especiallysucrose, glucose or methylglucose monooleates or dioleates, stearates,behenates, oleopalmitates, linoleates, linolenates and oleostearates.

An example that may be mentioned is the product sold under the nameGlucate® DO by the company Amerchol, which is a methylglucose dioleate.

As examples of preferable ester oils, mention may be made of, forexample, diisopropyl adipate, dioctyl adipate, 2-ethylhexyl hexanoate,ethyl laurate, cetyl octanoate, octyldodecyl octanoate, isodecylneopentanoate, myristyl propionate, 2-ethylhexyl 2-ethylhexanoate,2-ethylhexyl octanoate, 2-ethylhexyl caprylate/caprate, methylpalmitate, ethyl palmitate, isopropyl palmitate, dicaprylyl carbonate,isopropyl lauroyl sarcosinate, isononyl isononanoate, ethylhexylpalmitate, isohexyl laurate, hexyl laurate, isocetyl stearate, isopropylisostearate, isopropyl myristate, isodecyl oleate, glyceryltri(2-ethylhexanoate), pentaerythrityl tetra(2-ethylhexanoate),2-ethylhexyl succinate, diethyl sebacate, and mixtures thereof.

As examples of artificial triglycerides, mention may be made of, forexample, caproyl caprylyl glycerides, glyceryl trimyristate, glyceryltripalmitate, glyceryl trilinolenate, glyceryl trilaurate, glyceryltricaprate, glyceryl tricaprylate, glyceryl tri(caprate/caprylate) andglyceryl tri(caprate/caprylate/linolenate).

As examples of silicone oils, mention may be made of, for example,linear organopolysiloxanes such as dimethylpolysiloxane,methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like;cyclic organopolysiloxanes such as cyclohexasiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, and the like; and mixtures thereof.

Preferably, silicone oil is chosen from liquid polydialkylsiloxanes,especially liquid polydimethylsiloxanes (PDMS) and liquidpolyorganosiloxanes comprising at least one aryl group.

These silicone oils may also be organomodified. The organomodifiedsilicones that can be used according to the present invention aresilicone oils as defined above and comprise in their structure one ormore organofunctional groups attached via a hydrocarbon-based group.

Organopolysiloxanes are defined in greater detail in Walter Noll'sChemistry and Technology of Silicones (1968), Academic Press. They maybe volatile or non-volatile.

When they are volatile, the silicones are more particularly chosen fromthose having a boiling point of between 60° C. and 260° C., and evenmore particularly from:

(i) cyclic polydialkylsiloxanes comprising from 3 to 7 and preferably 4to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxanesold in particular under the name Volatile Silicone® 7207 by UnionCarbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxanesold under the name Volatile Silicone® 7158 by Union Carbide, Silbione®70045 V5 by Rhodia, and dodecamethylcyclopentasiloxane sold under thename Silsoft 1217 by Momentive Performance Materials, and mixturesthereof. Mention may also be made of cyclocopolymers of the type such asdimethylsiloxane/methylalkylsiloxane, such as Silicone Volatile® FZ 3109sold by the company Union Carbide, of formula:

Mention may also be made of mixtures of cyclic polydialkylsiloxanes withorganosilicon compounds, such as the mixture ofoctamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol(50/50) and the mixture of octamethylcyclotetrasiloxane andoxy-1,1′-bis(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentane; and

(ii) linear volatile polydialkylsiloxanes containing 2 to 9 siliconatoms and having a viscosity of less than or equal to 5×10⁻⁶ m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under thename SH 200 by the company Toray Silicone. Silicones belonging to thiscategory are also described in the article published in Cosmetics andToiletries, Vol. 91, January 76, pp. 27-32, Todd & Byers, VolatileSilicone Fluids for Cosmetics. The viscosity of the silicones ismeasured at 25° C. according to ASTM standard 445 Appendix C.

Non-volatile polydialkylsiloxanes may also be used. These non-volatilesilicones are more particularly chosen from polydialkylsiloxanes, amongwhich mention may be made mainly of polydimethylsiloxanes containingtrimethylsilyl end groups.

Among these polydialkylsiloxanes, mention may be made, in a non-limitingmanner, of the following commercial products:

-   -   the Silbione® oils of the 47 and 70 047 series or the Mirasil®        oils sold by Rhodia, for instance the oil 70 047 V 500 000;    -   the oils of the Mirasil® series sold by the company Rhodia;    -   the oils of the 200 series from the company Dow Corning, such as        DC200 with a viscosity of 60 000 mm²/s; and    -   the Viscasil® oils from General Electric and certain oils of the        SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polydimethylsiloxanes containingdimethylsilanol end groups known under the name dimethiconol (CTFA),such as the oils of the 48 series from the company Rhodia.

Among the silicones containing aryl groups, mention may be made ofpolydiarylsiloxanes, especially polydiphenylsiloxanes andpolyalkylarylsiloxanes such as phenyl silicone oil.

The phenyl silicone oil may be chosen from the phenyl silicones of thefollowing formula:

in which

R₁ to R₁₀, independently of each other, are saturated or unsaturated,linear, cyclic or branched C₁-C₃₀ hydrocarbon-based radicals, preferablyC₁-C₁₂ hydrocarbon-based radicals, and more preferably C₁-C₆hydrocarbon-based radicals, in particular methyl, ethyl, propyl or butylradicals, and

m, n, p and q are, independently of each other, integers 0 to 900inclusive, preferably 0 to 500 inclusive, and more preferably 0 to 100inclusive,

with the proviso that the sum n+m+q is other than 0.

Examples that may be mentioned include the products sold under thefollowing names:

-   -   the Silbione® oils of the 70 641 series from Rhodia;    -   the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;    -   the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;    -   the silicones of the PK series from Bayer, such as the product        PK20;    -   certain oils of the SF series from General Electric, such as SF        1023, SF 1154, SF 1250 and SF 1265.

As the phenyl silicone oil, phenyl trimethicone (R₁ to R₁₀ are methyl;p, q, and n=0; m=1 in the above formula) is preferable.

The organomodified liquid silicones may especially containpolyethyleneoxy and/or polypropyleneoxy groups. Mention may thus be madeof the silicone KF-6017 proposed by Shin-Etsu, and the oils Silwet® L722and L77 from the company Union Carbide.

Hydrocarbon oils may be chosen from:

-   -   linear or branched, optionally cyclic, C₆-C₁₆ lower alkanes.        Examples that may be mentioned include hexane, undecane,        dodecane, tridecane, and isoparaffins, for instance        isohexadecane, isododecane and isodecane; and    -   linear or branched hydrocarbons containing more than 16 carbon        atoms, such as liquid paraffins, liquid petroleum jelly,        polydecenes and hydrogenated polyisobutenes such as Parleam®,        and squalane.

As preferable examples of hydrocarbon oils, mention may be made of, forexample, linear or branched hydrocarbons such as isohexadecane,isododecane, squalane, mineral oil (e.g., liquid paraffin), paraffin,vaseline or petrolatum, naphthalenes, and the like; hydrogenatedpolyisobutene, isoeicosan, and decene/butene copolymer; and mixturesthereof.

The term “fatty” in the fatty alcohol means the inclusion of arelatively large number of carbon atoms. Thus, alcohols which have 4 ormore, preferably 6 or more, and more preferably 12 or more carbon atomsare encompassed within the scope of fatty alcohols. The fatty alcoholmay be saturated or unsaturated. The fatty alcohol may be linear orbranched.

The fatty alcohol may have the structure R—OH wherein R is chosen fromsaturated and unsaturated, linear and branched radicals containing from4 to 40 carbon atoms, preferably from 6 to 30 carbon atoms, and morepreferably from 12 to 20 carbon atoms. In at least one embodiment, R maybe chosen from C₁₂-C₂₀ alkyl and C₁₂-C₂₀ alkenyl groups. R may or maynot be substituted with at least one hydroxyl group.

As examples of the fatty alcohol, mention may be made of lauryl alcohol,cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol,undecylenyl alcohol, myristyl alcohol, octyldodecanol, hexyldecanol,oleyl alcohol, linoleyl alcohol, palmitoleyl alcohol, arachidonylalcohol, erucyl alcohol, and mixtures thereof.

It is preferable that the fatty alcohol be a saturated fatty alcohol.

Thus, the fatty alcohol may be selected from straight or branched,saturated or unsaturated C₆-C₃₀ alcohols, preferably straight orbranched, saturated C₆-C₃₀ alcohols, and more preferably straight orbranched, saturated C₁₂-C₂₀ alcohols.

The term “saturated fatty alcohol” here means an alcohol having a longaliphatic saturated carbon chain. It is preferable that the saturatedfatty alcohol be selected from any linear or branched, saturated C₆-C₃₀fatty alcohols. Among the linear or branched, saturated C₆-C₃₀ fattyalcohols, linear or branched, saturated C₁₂-C₂₀ fatty alcohols maypreferably be used. Any linear or branched, saturated C₁₆-C₂₀ fattyalcohols may be more preferably used. Branched C₁₆-C₂₀ fatty alcoholsmay be even more preferably used.

As examples of saturated fatty alcohols, mention may be made of laurylalcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenylalcohol, undecylenyl alcohol, myristyl alcohol, octyldodecanol,hexyldecanol, and mixtures thereof. In one embodiment, cetyl alcohol,stearyl alcohol, octyldodecanol, hexyldecanol, or a mixture thereof(e.g., cetearyl alcohol) as well as behenyl alcohol, can be used as asaturated fatty alcohol.

According to at least one embodiment, the fatty alcohol used in thecomposition according to the present invention is preferably chosen fromoctyldodecanol, hexyldecanol and mixtures thereof.

It is preferable that the (b) oil be chosen from polar oils, morepreferably from ester oils, artificial triglycerides and mixturesthereof, and even more preferably from ester oils, artificialtriglycerides and mixtures thereof other than organic lipophilic UVfilters, in particular ethylhexylmethoxycinnamate.

According to the present invention, the (b) oil may be surrounded by aplurality of the (a) particles or the (b) oil may be present in thehollow of a capsule formed by the (a) particles.

In other words, the (b) oil may be covered by the (a) particles, or acapsule formed by the (a) particles includes the (b) oil in the hollowof the capsule.

The (b) oil which is surrounded by the (a) particles or present in thehollow of the capsule formed by the (a) particles cannot directly makecontact with a keratin substance such as skin.

Thus, even if the (b) oil has a sticky or greasy feeling of use, thecomposition according to the present invention may not provide a stickyor greasy feeling of use.

The amount of the (b) oil(s) in the composition according to the presentinvention may be 0.01% by weight or more, preferably 0.1% by weight ormore, and more preferably 1% by weight or more, relative to the totalweight of the composition.

The amount of the (b) oil(s) in the composition according to the presentinvention may be 50% by weight or less, preferably 40% by weight orless, and more preferably 35% by weight or less, relative to the totalweight of the composition.

The amount of the (b) oil(s) in the composition according to the presentinvention may be from 0.01 to 50% by weight, preferably from 0.1 to 40%by weight, and more preferably from 1 to 35% by weight, relative to thetotal weight of the composition.

[Water]

The composition according to the present invention comprises (c) water.

The amount of the (c) water may be 40% by weight or more, preferably 50%by weight or more, and more preferably 60% by weight or more, relativeto the total weight of the composition.

The amount of the (c) water may be 90% by weight or less, preferably 80%by weight or less, and more preferably 70% by weight or less, relativeto the total weight of the composition.

The amount of the (c) water may be from 40 to 90% by weight, preferablyfrom 50 to 80% by weight, and more preferably from 60 to 70% by weight,relative to the total weight of the composition.

(Non-Polymeric Acid Having Two or More Acid Dissociation Constants)

The composition according to the present invention may include at leastone non-polymeric acid having two or more pKa values or salt(s) thereof,i.e., at least one non-polymeric acid having two or more aciddissociation constants or salt(s) thereof. The pKa value (aciddissociation constant) is well known to those skilled in the art, andshould be determined at a constant temperature such as 25° C.

The non-polymeric acid having two or more pKa values or salt(s) thereofcan be included in the (a) particle. The non-polymeric acid having twoor more pKa values can function as a crosslinker for the cationicpolymer, anionic polymer and amphoteric polymers.

The term “non-polymeric” here means that the acid is not obtained bypolymerizing two or more monomers. Therefore, the non-polymeric aciddoes not correspond to an acid obtained by polymerizing two or moremonomers such as polycarboxylic acid.

It is preferable that the molecular weight of the non-polymeric acidhaving two or more pKa values or salt(s) thereof is 1000 or less,preferably 800 or less, and more preferably 700 or less.

There is no limit to the type of the non-polymeric acid having two ormore pKa values or salt(s) thereof. Two or more different types ofnon-polymeric acids having two or more pKa values or salts thereof maybe used in combination. Thus, a single type of a non-polymeric acidhaving two or more pKa values or a salt thereof or a combination ofdifferent types of non-polymeric acids having two or more pKa values orsalts thereof may be used.

The term “salt” in the present specification means a salt formed byaddition of suitable base(s) to the non-polymeric acid having two ormore pKa values, which may be obtained from a reaction with thenon-polymeric acid having two or more pKa values with the base(s)according to methods known to those skilled in the art. As the salt,mention may be made of metal salts, for example salts with alkalinemetal such as Na and K, and salts with alkaline earth metal such as Mgand Ca, and ammonium salts.

The non-polymeric acid having two or more pKa values or salt(s) thereofmay be an organic acid or salt(s) thereof, and preferably a hydrophilicor water-soluble organic acid or salt(s) thereof.

The non-polymeric acid having two or more pKa values may have at leasttwo acid groups selected from the group consisting of a carboxylicgroup, a sulfuric group, a sulfonic group, a phosphoric group, aphosphonic group, a phenolic hydroxyl group, and a mixture thereof.

The non-polymeric acid having two or more pKa values may be anon-polymeric polyvalent acid.

The non-polymeric acid having two or more pKa values may be selectedfrom the group consisting of dicarboxylic acids, disulfonic acids, anddiphosphoric acids, and a mixture thereof.

The non-polymeric acid having two or more pKa values or salt(s) thereofmay be selected from the group consisting of oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, fumaric acid, maleic acid, malic acid,citric acid, aconitic acid, oxaloacetic acid, tartaric acid, and saltsthereof; aspartic acid, glutamic acid, and salts thereof;terephthalylidene dicamphor sulfonic acid or salts thereof (Mexoryl SX),Benzophenone-9; phytic acid, and salts thereof; Red 2 (Amaranth), Red102 (New Coccine), Yellow 5 (Tartrazine), Yellow 6 (Sunset Yellow FCF),Green 3 (Fast Green FCF), Blue 1 (Brilliant Blue FCF), Blue 2 (IndigoCarmine), Red 201 (Lithol Rubine B), Red 202 (Lithol Rubine BCA), Red204 (Lake Red CBA), Red 206 (Lithol Red CA), Red 207 (Lithol Red BA),Red 208 (Lithol Red SR), Red 219 (Brilliant Lake Red R), Red 220 (DeepMaroon), Red 227 (Fast Acid Magenta), Yellow 203 (Quinoline Yellow WS),Green 201 (Alizanine Cyanine Green F), Green 204 (Pyranine Conc), Green205 (Light Green SF Yellowish), Blue 203 (Patent Blue CA), Blue 205(Alfazurine FG), Red 401 (Violamine R), Red 405 (Permanent Re F5R), Red502 (Ponceau 3R), Red 503 (Ponceau R), Red 504 (Ponceau SX), Green 401(Naphtol Green B), Green 402 (Guinea Green B), and Black 401 (NaphtolBlue Black); folic acid, ascorbic acid, erythorbic acid, and saltsthereof; cystine and salts thereof; EDTA and salts thereof; glycyrrhizinand salts thereof; and a mixture thereof.

It may be preferable that the non-polymeric acid having two or more pKavalues or salt(s) thereof be selected from the group consisting ofterephthalylidene dicamphor sulfonic acid and salts thereof (MexorylSX), Yellow 6 (Sunset Yellow FCF), ascorbic acid, phytic acid and saltsthereof, and a mixture thereof.

The amount of the non-polymeric acid having two or more pKa values orsalt(s) thereof in the composition according to the present inventionmay be 0.0001% by weight or more, preferably 0.01% by weight or more,and more preferably 0.1% by weight or more, relative to the total weightof the composition.

The amount of the non-polymeric acid having two or more pKa values orsalt(s) thereof in the composition according to the present inventionmay be 30% by weight or less, preferably 20% by weight or less, and morepreferably 15% by weight or less, relative to the total weight of thecomposition.

The amount of the non-polymeric acid having two or more pKa values orsalt(s) thereof in the composition according to the present inventionmay be from 0.0001 to 30% by weight, preferably from 0.01 to 20% byweight, and more preferably from 0.1 to 15% by weight, relative to thetotal weight of the composition.

(Non-Polymeric Base Having Two or More Base Dissociation Constants)

The composition according to the present invention may include at leastone non-polymeric base having two or more pKb values or salt(s) thereof,i.e., at least one non-polymeric base having two or more basedissociation constants or salt(s) thereof. The pKb value (basedissociation constant) is well known to those skilled in the art, andshould be determined at a constant temperature such as 25° C.

The non-polymeric base having two or more pKb values or salt(s) thereofcan be included in the (a) particle. The non-polymeric base having twoor more pKb values can function as a crosslinker for the cationicpolymer, anionic polymer and amphoteric polymers.

The term “non-polymeric” here means that the base is not obtained bypolymerizing two or more monomers. Therefore, the non-polymeric basedoes not correspond to a base obtained by polymerizing two or moremonomers such as polyallylamine.

It is preferable that the molecular weight of the non-polymeric basehaving two or more pKb values or salt(s) thereof be 1000 or less,preferably 800 or less, and more preferably 700 or less.

There is no limit to the type of the non-polymeric base having two ormore pKb values or salt(s) thereof. Two or more different types ofnon-polymeric bases having two or more pKb values or salts thereof maybe used in combination. Thus, a single type of a non-polymeric basehaving two or more pKb values or a salt thereof or a combination ofdifferent types of non-polymeric bases having two or more pKb values orsalts thereof may be used.

The term “salt” in the present specification means a salt formed byaddition of suitable acid(s) to the non-polymeric base having two ormore pKb values, which may be obtained from a reaction with thenon-polymeric base having two or more pKb values with the acid(s)according to methods known to those skilled in the art. As the salt,mention may be made of ammonium salts, for example salts with inorganicacid such as HCl and HNO₃, and salts with organic acid such ascarboxylic acids and sulfonic acids.

The non-polymeric base having two or more pKb values or salt(s) thereofmay be an organic base or salt(s) thereof, and preferably a hydrophilicor water-soluble organic base or salt(s) thereof.

The non-polymeric base having two or more pKb values may have at leasttwo basic groups selected from the group consisting of an amino group, aguanidine group, a biguanide group, an imidazole group, an imino group,a pyridyl group and a mixture thereof.

The non-polymeric base having two or more pKb values may be selectedfrom the group consisting of non-polymeric diamines such asethylenediamine, propylenediamine, pentanediamine, hexanediamine, ureaand derivatives thereof and guanidine and derivatives thereof,non-polymeric polyamines such as spermine and spermidine, basic aminoacids, and a mixture thereof.

The non-polymeric base having two or more pKb values or salt(s) thereofmay be selected from the group consisting of arginine, lysine,histidine, cysteine, cystine, tyrosine, tryptophan, ornithine, and amixture thereof.

It may be preferable that the non-polymeric base having two or more pKbvalues or salt(s) thereof be selected from the group consisting ofarginine, lysine, histidine, and a mixture thereof.

The amount of the non-polymeric base having two or more pKb values orsalt(s) thereof in the composition according to the present inventionmay be 0.0001% by weight or more, preferably 0.01% by weight or more,and more preferably 0.1% by weight or more, relative to the total weightof the composition.

The amount of the non-polymeric base having two or more pKb values orsalt(s) thereof in the composition according to the present inventionmay be 30% by weight or less, preferably 20% by weight or less, and morepreferably 15% by weight or less, relative to the total weight of thecomposition.

The amount of the non-polymeric base having two or more pKb values orsalt(s) thereof in the composition according to the present inventionmay be from 0.0001 to 30% by weight, preferably from 0.01 to 20% byweight, and more preferably from 0.1 to 15% by weight, relative to thetotal weight of the composition.

[Hydrophobic Amino Acid]

The (a) particle in the composition according to the present inventionmay include (d) at least one hydrophobic amino acid other than the abovenon-polymeric acid having two or more pKa values or salt(s) thereof orthe above non-polymeric base having two or more pKb values or salt(s)thereof. Two or more hydrophobic amino acids may be used in combination.

The term “hydrophobic amino acid” may be selected from the groupconsisting of isoleucine, leucine, valine, methionine, phenylalanine,threonine, glycine, cysteine, alanine and mixtures thereof. It ispreferable that the (d) hydrophobic amino acid be selected from leucine,phenylalanine and mixtures thereof.

The (d) hydrophobic amino acid may be useful for controlling thehydrophobicity of the (a) particle which may influence the encapsulationability of the (a) particles, depending on the type of the (b) oil.

The amount of the (d) hydrophobic amino acid(s) in the compositionaccording to the present invention may be 0.001% by weight or more,preferably 0.01% by weight or more, and more preferably 0.1% by weightor more, relative to the total weight of the composition.

The amount of the (d) hydrophobic amino acid(s) in the compositionaccording to the present invention may be 10% by weight or less,preferably 5% by weight or less, and more preferably 1% by weight orless, relative to the total weight of the composition.

The amount of the (d) hydrophobic amino acid(s) in the compositionaccording to the present invention may be from 0.001 to 10% by weight,preferably from 0.01 to 5% by weight, and more preferably from 0.1 to 1%by weight, relative to the total weight of the composition.

[Oil Gelling Agent]

The composition according to the present invention may include (e) atleast one oil gelling agent. Two or more oil gelling agents may be usedin combination.

The (e) oil gelling agent (lipophilic thickener) can enhance thestability of the composition according to the present invention even ifthe oil in the composition is less polar or non-polar.

The (e) oil gelling agent may be chosen from gelling agents derived fromglutamic acid, gelling agents in polymeric form, and gelling agents inmineral form. The gelling agent includes agents that gel via chemicalreticulation and agents that gel via physical reticulation.

N-acyl glutamic acid derivatives may be used as gelling agents derivedfrom glutamic acid. N-acyl glutamic acid derivatives include N-acylglutamic acid amides and N-acyl glutamic acid esters. In one embodiment,N-acyl glutamic acid amides in which the acyl group represents a C₈ toC₂₂ alkyl chain are preferred.

Examples of N-acyl glutamic acid derivatives that may be mentionedinclude N-lauroyl-glutamic acid diethyl amide, N-lauroyl-glutamic aciddibutyl amide, N-lauroyl-glutamic acid dihexyl amide, N-lauroyl-glutamicacid dioctyl amide, N-lauroyl-glutamic acid didecyl amide,N-lauroyl-glutamic acid didodecyl amide, N-lauroyl-glutamic acidditetradecyl amide, N-lauroyl-glutamic acid dihexadecyl amide,N-lauroyl-glutamic acid distearyl amide, N-ethylhexanoyl-L-glutamic aciddibutyl amide, N-stearoyl-glutamic acid dibutyl amide,N-stearoyl-glutamic acid dihexyl amide, N-stearoyl-glutamic aciddiheptyl amide, N-stearoyl-glutamic acid dioctyl amide,N-stearoyl-glutamic acid didecyl amide, N-stearoyl-glutamic aciddidodecyl amide, N-stearoyl-glutamic acid ditetradecyl amide,N-stearoyl-glutamic acid dihexadecyl amide, N-stearoyl-glutamic aciddistearyl amide and mixtures thereof, and more preferred isN-lauroyl-glutamic acid dibutyl amide, N-stearyl-glutamic acid dihexylamide, and mixtures thereof.

The gelling agent is preferably N-acyl glutamic acid dialkylamide, andmore preferably N-lauroyl-L-glutamic acid dibutylamide (INCI: dibutyllauroyl glutamide), manufactured or sold by Ajinomoto under the nameGP-1 and N-ethylhexanoyl-L-glutamic acid dibutylamide (INCI: dibutylethylhexanoyl glutamide), manufactured or sold by Ajinomoto under thename EB-21.

Lipophilic polyamide polymers may be used as gelling agents in polymericform. As lipophilic polyamide polymers, mention may be made ofpolyamides branched with pendent fatty chains and/or terminal fattychains containing from 12 to 120 carbon atoms and in particular from 12to 68 carbon atoms, the terminal fatty chains being bonded to thepolyamide backbone via ester groups. These polymers are more especiallythose described in document U.S. Pat. No. 5,783,657 from the companyUnion Camp. In particular, mention may be made of the polymers of whichthe INCI name is “ethylenediamine/stearyl dimer dilinoleate copolymer”and “ethylenediamine/stearyl dimer tallate copolymer”.

By way of examples of gelling agents, mention may be made of thecommercial products sold by the company Bush Boake Allen under the namesUniclear 80, Uniclear 100, Uniclear 80 V, Uniclear 100 V and Uniclear100 VG. They are sold, respectively, in the form of a gel at 80% (withrespect to active material) in a mineral oil and at 100% (with respectto active material).

Modified clays may be used as gelling agents, examples of which includehectorites modified with an ammonium chloride of a C₁₀ to C₂₂ fattyacid, such as bentonite modified with distearyldimethylammoniumchloride, also known as quaternium-18 bentonite, such as the productssold or made under the names Bentone 34 and Bentone 38 VCG by thecompany Rheox, Claytone XL, Claytone 34 and Claytone 40 sold or made bythe company Southern Clay, the modified clays known under the namequaternium-18 benzalkonium bentonites and sold or made under the namesClaytone HT, Claytone GR and Claytone PS by the company Southern Clay,the clays modified with stearyldimethylbenzoylammonium chloride, knownas stearalkonium bentonites, such as the products sold or made under thenames Claytone APA and Claytone AF by the company Southern Clay, andBaragel 24 sold or made by the company Rheox.

The amount of the (e) oil gelling agent(s) in the composition accordingto the present invention may be 0.001% by weight or more, preferably0.01% by weight or more, and more preferably 0.1% by weight or more,relative to the total weight of the composition.

The amount of the (e) oil gelling agent(s) in the composition accordingto the present invention may be 10% by weight or less, preferably 5% byweight or less, and more preferably 1% by weight or less, relative tothe total weight of the composition.

The amount of the (e) oil gelling agent(s) in the composition accordingto the present invention may be from 0.001 to 10% by weight, preferablyfrom 0.01 to 5% by weight, and more preferably from 0.1 to 1% by weight,relative to the total weight of the composition.

[Cosmetic Active Ingredient]

The composition according to the present invention may comprise at leastone (additional) cosmetic active ingredient in addition to the (b) oil.There is no limitation to the additional cosmetic active ingredient aslong as it is not the (b) oil. Two or more additional cosmetic activeingredients may be used in combination. Thus, a single type ofadditional cosmetic active ingredient or a combination of differenttypes of additional cosmetic active ingredients may be used.

Among the additional cosmetic active ingredients to be used, mention maybe made of hydrophobic or water-insoluble UV filters, anti-oxidants,cleansing agents, free radical scavengers, moisturizers, whiteningagents, liporegulators, anti-acne agents, antidandruff agents,anti-aging agents, softeners, anti-wrinkle agents, keratolitic agents,fresheners, antibacterial agents, antifungal agents, antiperspirants,deodorants, skin conditioners, anesthetics, nourishing agents, and sebumabsorbers or moisture absorbers.

The composition according to the present invention may comprise theadditional cosmetic active ingredient(s) in an amount of from 0.01 to50% by weight, preferably from 0.1 to 40% by weight, more preferablyfrom 1 to 30% by weight, and even more preferably 2 to 20% by weight,relative to the total weight of the composition.

(Hydrophobic or Water-Insoluble UV Filter)

According to a preferred embodiment of the present invention, theadditional cosmetic active ingredient may be selected from hydrophobicor water-insoluble UV filters.

There is no limit to the type of the hydrophobic or water-insoluble UVfilter. Two or more types of hydrophobic or water-insoluble UV filtersmay be used in combination. Thus, a single type of hydrophobic orwater-insoluble UV filter or a combination of different types ofhydrophobic or water-insoluble UV filters may be used. The hydrophobicor water-insoluble UV filter can be selected from the group consistingof an inorganic UV filter, a hydrophobic or water-insoluble organic UVfilter, and a mixture thereof.

(Inorganic UV Filter)

The composition according to the present invention may comprise at leastone inorganic UV filter. If two or more inorganic UV filters are used,they may be the same or different, preferably the same.

The inorganic UV filter used for the present invention may be active inthe UV-A and/or UV-B region. The inorganic UV filter used for thepresent invention is water-insoluble in solvents such as water andethanol commonly used in cosmetics, but may be hydrophilic and/orlipophilic.

It is preferable that the inorganic UV filter be in the form of a fineparticle such that the mean (primary) particle diameter thereof rangesfrom 1 nm to 50 nm, preferably 5 nm to 40 nm, and more preferably 10 nmto 30 nm. The mean (primary) particle size or mean (primary) particlediameter here is an arithmetic mean diameter.

The inorganic UV filter can be selected from the group consisting ofsilicon carbide, metal oxides which may or may not be coated, andmixtures thereof.

Preferably, the inorganic UV filters may be selected from pigments (meansize of the primary particles: generally from 5 nm to 50 nm, preferablyfrom 10 nm to 50 nm) formed of metal oxides, such as, for example,pigments formed of titanium oxide (amorphous or crystalline in therutile and/or anatase form), iron oxide, zinc oxide, zirconium oxide orcerium oxide, which are all UV photoprotective agents that are wellknown per se. Preferably, the inorganic UV filters may be selected fromtitanium oxide, zinc oxide, and more preferably titanium oxide.

The inorganic UV filter may or may not be coated. The inorganic UVfilter may have at least one coating. The coating may comprise at leastone compound selected from the group consisting of alumina, silica,aluminum hydroxide, silicones, silanes, fatty acids or salts thereof(such as sodium, potassium, zinc, iron, or aluminum salts), fattyalcohols, lecithin, amino acids, polysaccharides, proteins,alkanolamines, waxes such as beeswax, (meth)acrylic polymers, organic UVfilters, and (per)fluoro compounds.

It is preferable for the coating to include at least one organic UVfilter. As the organic UV filter in the coating, a dibenzoylmethanederivative such as butyl methoxydibenzoylmethane (Avobenzone) and2,2′-Methylenebis[6-(2H-Benzotriazol-2-yl)-4-(1,1,3,3-Tetramethyl-Butyl)Phenol](Methylene Bis-Benzotriazolyl Tetramethylbutylphenol) marketed as“TINOSORB M” by BASF may be preferable.

In a known manner, the silicones in the coating(s) may be organosiliconpolymers or oligomers comprising a linear or cyclic and branched orcross-linked structure, of variable molecular weight, obtained bypolymerization and/or polycondensation of suitable functional silanesand essentially composed of repeated main units in which the siliconatoms are connected to one another via oxygen atoms (siloxane bond),optionally substituted hydrocarbon radicals being connected directly tosaid silicon atoms via a carbon atom.

The term “silicones” also encompasses silanes necessary for theirpreparation, in particular alkylsilanes.

The silicones used for the coating(s) can preferably be selected fromthe group consisting of alkylsilanes, polydialkylsiloxanes, andpolyalkylhydrosiloxanes. More preferably still, the silicones areselected from the group consisting of octyltrimethylsilanes,polydimethylsiloxanes, and polymethylhydrosiloxanes.

Of course, the inorganic UV filters made of metal oxides may, beforetheir treatment with silicones, have been treated with other surfacingagents, in particular, with cerium oxide, alumina, silica, aluminumcompounds, silicon compounds, or their mixtures.

The coated inorganic UV filter may have been prepared by subjecting theinorganic UV filter to one or more surface treatments of a chemical,electronic, mechanochemical, and/or mechanical nature with any of thecompounds as described above, as well as polyethylenes, metal alkoxides(titanium or aluminum alkoxides), metal oxides, sodiumhexametaphosphate, and those shown, for example, in Cosmetics &Toiletries, February 1990, Vol. 105, pp. 53-64.

The coated inorganic UV filters may be titanium oxides coated with:

silica, such as the product “Sunveil” from Ikeda;

silica and iron oxide, such as the product “Sunveil F” from Ikeda;

silica and alumina, such as the products “Microtitanium Dioxide MT 500SA” from Tayca,

“Tioveil” from Tioxide, and “Mirasun TiW 60” from Rhodia;

alumina, such as the products “Tipaque TTO-55 (B)” and “Tipaque TTO-55(A)” from Ishihara, and “UVT 14/4” from Kemira;

alumina and aluminum stearate, such as the product “MicrotitaniumDioxide MT 100 T, MT 100 TX, MT 100 Z or MT-01” from Tayca, the products“Solaveil CT-10 W” and “Solaveil CT 100” from Uniqema, and the product“Eusolex T-AVO” from Merck;

alumina and aluminum laurate, such as the product “Microtitanium DioxideMT 100 S” from Tayca;

iron oxide and iron stearate, such as the product “Microtitanium DioxideMT 100 F” from Tayca;

zinc oxide and zinc stearate, such as the product “BR351” from Tayca;

silica and alumina and treated with a silicone, such as the products“Microtitanium Dioxide MT 600 SAS”, “Microtitanium Dioxide MT 500 SAS”,and “Microtitanium Dioxide MT 100 SAS” from Tayca;

silica, alumina, and aluminum stearate and treated with a silicone, suchas the product “STT-30-DS” from Titan Kogyo;

silica and treated with a silicone, such as the product “UV-Titan X 195”from Kemira; alumina and treated with a silicone, such as the products“Tipaque TTO-55 (S)” from Ishihara or “UV Titan M 262” from Kemira;

triethanolamine, such as the product “STT-65-S” from Titan Kogyo;

stearic acid, such as the product “Tipaque TTO-55 (C)” from Ishihara; or

sodium hexametaphosphate, such as the product “Microtitanium Dioxide MT150 W” from Tayca.

Other titanium oxide pigments treated with a silicone are preferablyTiO₂ treated with octyltrimethylsilane and for which the mean size ofthe individual particles is from 25 and 40 nm, such as that marketedunder the trademark “T 805” by Degussa Silices, TiO₂ treated with apolydimethylsiloxane and for which the mean size of the individualparticles is 21 nm, such as that marketed under the trademark “70250Cardre UF TiO₂Si₃” by Cardre, and anatase/rutile TiO₂ treated with apolydimethylhydrosiloxane and for which the mean size of the individualparticles is 25 nm, such as that marketed under the trademark“Microtitanium Dioxide USP Grade Hydrophobic” by Color Techniques.

Preferably, the following coated TiO₂ can be used as the coatedinorganic UV filter: Stearic acid (and) Aluminum Hydroxide (and) TiO₂,such as the product “MT-100 TV” from Tayca, with a mean primary particlediameter of 15 nm;

Dimethicone (and) Stearic Acid (and) Aluminum Hydroxide (and) TiO₂, suchas the product “SA-TTO-S4” from Miyoshi Kasei, with a mean primaryparticle diameter of 15 nm; Silica (and) TiO₂, such as the product“MT-100 WP” from Tayca, with a mean primary particle diameter of 15 nm;

Dimethicone (and) Silica (and) Aluminum Hydroxide (and) TiO₂, such asthe product “MT-Y02” and “MT-Y-110 M3 S” from Tayca, with a mean primaryparticle diameter of 10 nm; Dimethicone (and) Aluminum Hydroxide (and)TiO₂, such as the product “SA-TTO-S3” from Miyoshi Kasei, with a meanprimary particle diameter of 15 nm;

Dimethicone (and) Alumina (and) TiO₂, such as the product “UV TITANM170” from Sachtleben, with a mean primary particle diameter of 15 nm;and

Silica (and) Aluminum Hydroxide (and) Alginic Acid (and) TiO₂, such asthe product “MT-100 AQ” from Tayca, with a mean primary particlediameter of 15 nm.

In terms of UV filtering ability, TiO₂ coated with at least one organicUV filter is more preferable. For example, Avobenzone (and) Stearic Acid(and) Aluminum Hydroxide (and) TiO₂, such as the product “HXMT-100ZA”from Tayca, with a mean primary particle diameter of 15 nm, can be used.

The uncoated titanium oxide pigments are, for example, marketed by Taycaunder the trademarks “Microtitanium Dioxide MT500B” or “MicrotitaniumDioxide MT600B”, by Degussa under the trademark “P 25”, by Wacker underthe trademark “Oxyde de titane transparent PW”, by Miyoshi Kasei underthe trademark “UFTR”, by Tomen under the trademark “ITS”, and by Tioxideunder the trademark “Tioveil AQ”.

The uncoated zinc oxide pigments are, for example:

those marketed under the trademark “Z-cote” by Sunsmart;

those marketed under the trademark “Nanox” by Elementis; and thosemarketed under the trademark “Nanogard WCD 2025” by NanophaseTechnologies.

The coated zinc oxide pigments are, for example:

those marketed under the trademark “Oxide Zinc CS-5” by Toshiba (ZnOcoated with polymethylhydrosiloxane);

those marketed under the trademark “Nanogard Zinc Oxide FN” by NanophaseTechnologies (as a 40% dispersion in Finsolv TN, C₁₂-C₁₅ alkylbenzoate);

those marketed under the trademark “Daitopersion Zn-30” and“Daitopersion Zn-50” by Daito (dispersions in oxyethylenatedpolydimethylsiloxane/cyclopolymethylsiloxane comprising 30% or 50% ofzinc nano-oxides coated with silica and polymethylhydrosiloxane); thosemarketed under the trademark “NFD Ultrafine ZnO” by Daikin (ZnO coatedwith phosphate of perfluoroalkyl and a copolymer based onperfluoroalkylethyl as a dispersion in cyclopentasiloxane);

those marketed under the trademark “SPD-Z1” by Shin-Etsu (ZnO coatedwith a silicone-grafted acrylic polymer dispersed incyclodimethylsiloxane);

those marketed under the trademark “Escalol Z100” by ISP(alumina-treated ZnO dispersed in an ethylhexylmethoxycinnamate/PVP-hexadecene copolymer/methicone mixture);

those marketed under the trademark “Fuji ZnO-SMS-10” by Fuji Pigment(ZnO coated with silica and polymethylsilsesquioxane); and thosemarketed under the trademark “Nanox Gel TN” by Elementis (ZnO dispersedat 55% in C₁₂-C₁₅ alkyl benzoate with hydroxystearic acidpolycondensate).

The uncoated cerium oxide pigments are marketed, for example, under thetrademark “Colloidal Cerium Oxide” by Rhone-Poulenc.

The uncoated iron oxide pigments are, for example, marketed by Amaudunder the trademarks “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45BL AQ”, “Nanogard FE 45R AQ”, and “Nanogard WCD 2006 (FE 45R)”, or byMitsubishi under the trademark “TY-220”.

The coated iron oxide pigments are, for example, marketed by Arnaudunder the trademarks “Nanogard WCD 2008 (FE 45B FN)”, “Nanogard WCD 2009(FE 45B 556)”, “Nanogard FE 45 BL 345”, and “Nanogard FE 45 BL”, or byBASF under the trademark “Oxyde de fer transparent”.

Mention may also be made of mixtures of metal oxides, in particular, oftitanium dioxide and of cerium dioxide, including a mixture of equalweights of titanium dioxide coated with silica and of cerium dioxidecoated with silica marketed by Ikeda under the trademark “Sunveil A”,and also a mixture of titanium dioxide and of zinc dioxide coated withalumina, with silica and with silicone, such as the product “M 261”marketed by Kemira, or coated with alumina, with silica, and withglycerol, such as the product “M 211” marketed by Kemira.

Coated inorganic UV filters are preferable, because the UV filteringeffects of the inorganic UV filters can be enhanced. In addition, thecoating(s) may help uniformly or homogeneously disperse the UV filtersin the composition according to the present invention.

If inorganic UV filter(s) in the form of fine particles is/are used, afilm according to the present invention which can be prepared from thecomposition according to the present invention may also have an effectof not providing a white appearance but a transparent or clearappearance, because the fine particles of the inorganic UV filters donot aggregate but can be spread uniformly or homogeneously in the film.It should be noted that free fine particles of inorganic UV filter(s)easily aggregate to give a white appearance to the skin.

(Hydrophobic or Water-Insoluble Organic UV Filter)

The composition according to the present invention may comprise at leastone hydrophobic or water-insoluble organic UV filter. If two or morehydrophobic or water-insoluble organic UV filters are used, they may bethe same or different, preferably the same.

The hydrophobic or water-insoluble organic UV filter used for thepresent invention may be active in the UV-A and/or UV-B region. Thehydrophobic or water-insoluble organic UV filter may be lipophilic.

The hydrophobic or water-insoluble organic UV filter may be solid orliquid. The terms “solid” and “liquid” mean solid and liquid,respectively, at 25° C. under 1 atm.

The hydrophobic or water-insoluble organic UV filter can be selectedfrom the group consisting of anthranilic compounds; dibenzoylmethanecompounds; cinnamic compounds; salicylic compounds; camphor compounds;benzophenone compounds; β,β-diphenylacrylate compounds; triazinecompounds; benzotriazole compounds; benzalmalonate compounds;benzimidazole compounds; imidazoline compounds; bis-benzoazolylcompounds; p-aminobenzoic acid (PABA) compounds;methylenebis(hydroxyphenylbenzotriazole) compounds; benzoxazolecompounds; screening polymers and screening silicones; dimers derivedfrom α-alkylstyrene; 4,4-diarylbutadiene compounds; guaiazulene andderivatives thereof; rutin and derivatives thereof; and mixturesthereof.

Mention may be made, as examples of the hydrophobic or water-insolubleorganic UV filter(s), of those denoted below under their INCI names, andmixtures thereof.

-   -   Anthranilic compounds: Menthyl anthranilate, marketed under the        trademark “Neo Heliopan MA” by Haarmann and Reimer.    -   Dibenzoylmethane compounds: Butyl methoxydibenzoylmethane,        marketed in particular under the trademark “Parsol 1789” by        Hoffmann-La Roche; and isopropyl dibenzoylmethane.    -   Cinnamic compounds: Ethylhexyl methoxycinnamate, marketed in        particular under the trademark “Parsol MCX” by Hoffmann-La        Roche; isopropyl methoxycinnamate; isopropoxy methoxycinnamate;        isoamyl methoxycinnamate, marketed under the trademark “Neo        Heliopan E 1000” by Haarmann and Reimer; cinoxate        (2-ethoxyethyl-4-methoxy cinnamate); DEA methoxycinnamate;        diisopropyl methylcinnamate; and glyceryl ethylhexanoate        dimethoxycinnamate.    -   Salicylic compounds: Homosalate (homomentyl salicylate),        marketed under the trademark “Eusolex HMS” by Rona/EM        Industries; ethylhexyl salicylate, marketed under the trademark        “Neo Heliopan OS” by Haarmann and Reimer; glycol salicylate;        butyloctyl salicylate; phenyl salicylate; dipropyleneglycol        salicylate, marketed under the trademark “Dipsal” by Scher; and        TEA salicylate, marketed under the trademark “Neo Heliopan TS”        by Haarmann and Reimer.    -   Camphor compounds, in particular, benzylidenecamphor        derivatives: 3-benzylidene camphor, manufactured under the        trademark “Mexoryl SD” by Chimex; 4-methylbenzylidene camphor,        marketed under the trademark “Eusolex 6300” by Merck;        benzylidene camphor sulfonic acid, manufactured under the        trademark “Mexoryl SL” by Chimex; camphor benzalkonium        methosulfate, manufactured under the trademark “Mexoryl SO” by        Chimex; and polyacrylamidomethyl benzylidene camphor,        manufactured under the trademark “Mexoryl SW” by Chimex.    -   Benzophenone compounds: Benzophenone-1        (2,4-dihydroxybenzophenone), marketed under the trademark        “Uvinul 400” by BASF; benzophenone-2 (Tetrahydroxybenzophenone),        marketed under the trademark “Uvinul D50” by BASF;        Benzophenone-3 (2-hydroxy-4-methoxybenzophenone) or oxybenzone,        marketed under the trademark “Uvinul M40” by BASF;        benzophenone-4 (hydroxymethoxy benzophonene sulfonic acid),        marketed under the trademark “Uvinul MS40” by BASF;        benzophenone-5 (Sodium hydroxymethoxy benzophenone Sulfonate);        benzophenone-6 (dihydroxy dimethoxy benzophenone); marketed        under the trademark “Helisorb 11” by Norquay; benzophenone-8,        marketed under the trademark “Spectra-Sorb UV-24” by American        Cyanamid; benzophenone-9 (Disodium dihydroxy dimethoxy        benzophenonedisulfonate), marketed under the trademark “Uvinul        DS-49” by BASF; benzophenone-12, and n-hexyl        2-(4-diethylamino-2-hydroxybenzoyl)benzoate (UVINUL A+ by BASF).    -   β,β-Diphenylacrylate compounds: Octocrylene, marketed in        particular under the trademark “Uvinul N539” by BASF; and        Etocrylene, marketed in particular under the trademark “Uvinul        N35” by BASF.    -   Triazine compounds: Diethylhexyl butamido triazone, marketed        under the trademark “Uvasorb HEB” by Sigma 3V;        2,4,6-tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine,        bis-ethylhexyloxyphenol methoxyphenyl triazine marketed under        the trademark «TINOSORB S» by CIBA GEIGY, and ethylhexyl        triazone marketed under the trademark «UVINUL T150 » by BASF.    -   Benzotriazole compounds, in particular, phenylbenzotriazole        derivatives: 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylpheno,        branched and linear; and those described in U.S. Pat. No.        5,240,975.    -   Benzalmalonate compounds: Dineopentyl 4′-methoxybenzalmalonate,        and polyorganosiloxane comprising benzalmalonate functional        groups, such as polysilicone-15, marketed under the trademark        “Parsol SLX” by Hoffmann-LaRoche.    -   Benzimidazole compounds, in particular, phenylbenzimidazole        derivatives.    -   Imidazoline compounds: Ethylhexyl dimethoxybenzylidene        dioxoimidazoline propionate.    -   Bis-benzoazolyl compounds: The derivatives as described in        EP-669,323 and U.S. Pat. No. 2,463,264.    -   Para-aminobenzoic acid compounds: PABA (p-aminobenzoic acid),        ethyl PABA, Ethyl dihydroxypropyl PABA, pentyl dimethyl PABA,        ethylhexyl dimethyl PABA, marketed in particular under the        trademark “Escalol 507” by ISP, glyceryl PABA, and PEG-25 PABA,        marketed under the trademark “Uvinul P25” by BASF.    -   Methylene bis-(hydroxyphenylbenzotriazol) compounds, such as        2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-methyl-phenol]        marketed in the solid form under the trademark “Mixxim BB/200”        by Fairmount Chemical,        2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]        marketed in the micronized form in aqueous dispersion under the        trademark “Tinosorb M” by BASF, or under the trademark “Mixxim        BB/100” by Fairmount Chemical, and the derivatives as described        in U.S. Pat. Nos. 5,237,071, 5,166,355, GB-2,303,549,        DE-197,26,184 and EP-893,119, and

Drometrizole trisiloxane, marketed under the trademark “Silatrizole” byRhodia Chimie or “Mexoryl XL” by L'Oreal, as represented below.

-   -   Benzoxazole compounds: 2,4-bis[5-1        (dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,        marketed under the trademark of Uvasorb K2A by Sigma 3V.    -   Screening polymers and screening silicones: The silicones        described in WO 93/04665.    -   Dimers derived from α-alkylstyrene: The dimers described in        DE-19855649.    -   4,4-Diarylbutadiene compounds:        1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene.

It is preferable that the hydrophobic or water-insoluble organic UVfilter(s) be selected from the group consisting of:

butyl methoxydibenzoylmethane, ethylhexyl methoxycinnamate, homosalate,ethylhexyl salicylate, octocrylene, benzophenone-3, benzophenone-4,benzophenone-5, n-hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,1,1′-(1,4-piperazinediyl)bis[1-[2-[4-(diethylamino)-2-hydroxybenzoyl]phenyl]-methanone4-methylbenzylidene camphor, ethylhexyl triazone,bis-ethylhexyloxyphenol methoxyphenyl triazine, diethylhexyl butamidotriazone, 2,4,6-tris(dineopentyl 4′-aminobenzalmalonate)-s-triazine,2,4,6-tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,2,4-bis-(n-butyl4′-aminobenzalmalonate)-6-[(3-{1,3,3,3-tetramethyl-1-[(trimethylsilyloxy]disiloxanyl}propyl)amino]-s-triazine,2,4,6-tris-(di-phenyl)-triazine, 2,4,6-tris-(ter-phenyl)-triazine,methylene bis-benzotriazolyl tetramethylbutylphenol, drometrizoletrisiloxane, polysilicone-15, dineopentyl 4′-methoxybenzalmalonate,1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-bis[5-1(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,camphor benzylkonium methosulfate and mixtures thereof.

(Whitening Agent)

According to a preferred embodiment of the present invention, thecosmetic active ingredient may be selected from whitening agents.

There is no limit to the type of whitening agent. Two or more types ofwhitening agents may be used in combination. Thus, a single type ofwhitening agent or a combination of different types of whitening agentsmay be used.

As examples of the whitening agent, mention may be made of ascorbic acidor derivatives thereof, kojic acid or derivatives thereof, tranexamicacid or derivatives thereof, resorcinol or derivatives thereof,alkoxysalicylic acid or salts thereof, adenosine phosphate or saltsthereof, hydroquinone or glycosides thereof or derivatives thereof,glutathione, 4-(4-hydroxyphenyl)-2-butanol, magnolignan(5,5′-dipropyl-biphenyl-2,2′-diol), chamomilla recutita, and the like.

Ascorbic acid has a D-configuration or L-configuration, and theL-configuration one is preferably employed. Ascorbic acid is alsoreferred to as vitamin C, and has effects of inhibiting the productionof melanin due to the strong reduction effects of ascorbic acid. Thederivatives of ascorbic acid may be salts of ascorbic acid, and thesalts of ascorbic acid are preferably selected from sodium ascorbate,magnesium ascorbyl phosphate, and sodium ascorbyl phosphate. Thederivatives of ascorbic acids may be glycosides of ascorbic acid oresters of ascorbic acid. As an example of glycosides of ascorbic acid,mention may be made of, for example, ascorbyl glucoside. As examples ofesters of ascorbic acid, mention may be made of, for example, silylascorbate, tocopheryl ascorbate, and alkyl ascorbate. As the alkylascorbate, methyl ascorbate or ethyl ascorbate is preferably used. Inparticular, ascorbyl glucoside is preferable. Ascorbic acid orderivatives thereof can be used alone or in combination with two or moretypes thereof.

As detailed examples of derivatives of ascorbic acid, mention may bemade of, for example, 5,6-di-O-dimethylsilyl ascorbate, which iscommercially available as PRO-AA from Exsymol SAM;dl-alpha-tocopheryl-2-1-ascorbyl phosphate which is commerciallyavailable as SEPIVITAL EPC from Senju Pharmaceutical Co., Ltd.; sodiumascorbyl phosphate which is commercially available as Stay-C 50 fromRoche; ascorbyl glucoside which is commercially available fromHayashibara Biochemical Labs., Inc.; 3-O-ethyl ascorbic acid; and thelike.

Ascorbic acid or the derivative thereof is preferably used incombination with a copolymer of styrene and maleic anhydride. Inparticular, at least one part of the maleic anhydride unit of theaforementioned copolymer is preferably hydrolyzed. The aforementionedhydrolyzed maleic anhydride unit may be in the form of an alkaline saltsuch as a sodium salt, a potassium salt, a lithium salt, or the like.The aforementioned maleic anhydride unit preferably occupies 0.4 to 0.9mol per one mol of the entire copolymer, and a ratio of the maleicanhydride unit and the styrene unit is preferably 50:50. In particular,it is preferable that the ratio of the maleic anhydride unit and thestyrene unit be preferably 50:50, and the ammonium salt or sodium saltbe used. By employing ascorbic acid or the derivative thereof incombination with the aforementioned copolymer, stability of ascorbicacid or the derivative thereof is improved. As the aforementionedcopolymer, for example, a copolymer of styrene and maleic anhydride(50/50) in the form of an ammonium salt in a concentration of 30% inwater, which is commercially available as product number SMA 1000 H(trademark) from Atofina Chemicals Inc.; or a copolymer of styrene andmaleic anhydride (50/50) in the form of a sodium salt in a concentrationof 40% in water, which is commercially available as product number SMA1000 H Na (trademark) from Atofina Chemicals Inc., can be used. Theaforementioned copolymer is used in a concentration ranging from 0.1 to20% by weight, and preferably ranging from 0.1 to 10% by weight, withrespect to the total weight of the whitening agent for topicalapplication.

As an example of derivatives of kojic acid, mention may be made of, forexample, kojic acid glucoside.

As examples of derivatives of tranexamic acid, mention may be made ofdimers of tranexamic acid (such as hydrochloric acidtrans-4-(trans-aminomethylcyclohexanecarbonyl)aminomethylcyclohexanecarboxylic acid), esters of tranexamic acid and hydroquinone (such as4′-hydroxyphenyl trans-4-aminomethylcyclohexane carboxylate), esters oftranexamic acid and gentisic acid (such as2-(trans-4-aminomethylcyclohexanecarbonyloxy)-5-hydroxybenzoic acid andsalts thereof), tranexamic amides (such astrans-4-aminomethylcyclohexanecarboxylic acid methylamide and saltsthereof, trans-4-(p-methoxybenzoyl)aminomethylcyclohexane carboxylicacid and salts thereof, and trans-4-guanidinomethylcyclohexanecarboxylic acid and salts thereof), and the like.

As examples of derivatives of resorcinol, mention may be made of, forexample, 4-n-butylresorcinol (Rucinol) and the like.

An alkoxysalicylic acid is a compound in which any one of the hydrogenatoms in the 3-position, the 4-position, or the 5-position of salicylicacid is substituted by an alkoxy group. The aforementioned alkoxy groupis preferably any one of a methoxy group, an ethoxy group, a propoxygroup, an isopropoxy group, a butoxy group, and an isobutoxy group, andis more preferably a methoxy group or an ethoxy group. As examples ofthe compound, mention may be made of, for example, 3-methoxysalicylicacid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylicacid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid,4-butoxysalicylic acid, 5-methoxysalicylic acid, 5-ethoxysalicylic acid,5-propoxysalicylic acid, and the like. Salts of the alkoxysalicylicacids are not particularly limited. As examples thereof, mention may bemade of, for example, alkali metal salts or alkaline earth metal saltssuch as sodium salts, potassium salts, calcium salts, and the like,ammonium salts, amino acid salts, and the like. A potassium salt of4-methoxysalicylic acid is preferable.

As examples of adenosine phosphate or salts thereof, mention may be madeof, for example, disodium adenosine phosphate, and the like.

As examples of glycosides of hydroquinone, mention may be made of, forexample, hexose glycosides such as hydroquinone alpha-D-glucose,hydroquinone beta-D-glucose, hydroquinone alpha-L-glucose, hydroquinonebeta-L-glucose, hydroquinone alpha-D-galactose, hydroquinonebeta-D-galactose, hydroquinone alpha-L-galactose, hydroquinonebeta-L-galactose, and the like; pentose glycosides such as hydroquinonealpha-D-ribose, hydroquinone beta-D-ribose, hydroquinone alpha-L-ribose,hydroquinone beta-L-ribose, hydroquinone alpha-D-arabinose, hydroquinonebeta-D-arabinose, hydroquinone alpha-L-arabinose, hydroquinonebeta-L-arabinose, and the like; aminosugar glycosides such ashydroquinone alpha-D-glucosamine, hydroquinone beta-D-glucosamine,hydroquinone alpha-L-glucosamine, hydroquinone beta-L-glucosamine,hydroquinone alpha-D-galactosamine, hydroquinone beta-D-galactosamine,hydroquinone alpha-L-galactosamine, hydroquinone beta-L-galactosamine,and the like; urocanic acid glycosides such as hydroquinonealpha-D-glucuronic acid, hydroquinone beta-D-glucuronic acid,hydroquinone alpha-L-glucuronic acid, hydroquinone beta-L-glucuronicacid, hydroquinone alpha-D-galacturonic acid, hydroquinonebeta-D-galacturonic acid, hydroquinone alpha-L-galacturonic acid,hydroquinone beta-L-galacturonic acid, and the like; and the like. Amongthese compounds, hydroquinone beta-D-glucose (hereinafter, referred toas “arbutin”) is preferable. As examples of derivatives of hydroquinoneor glycosides thereof, mention may be made of, for example, salts ofhydroquinone or glycosides thereof. In particular, as examples ofarbutin derivatives, mention may be made of, for example,6-O-caffeoylarbutin, and the like.

As the whitening active ingredients, in particular, L-ascorbic acid orderivatives thereof, kojic acid or derivatives thereof, tranexamic acidor derivatives thereof, arbutin or derivatives thereof, and Rucinol arepreferable, and ascorbic acid derivatives such as 3-O-ethyl L-ascorbicacid and L-ascorbic acid glucoside are more preferable.

[pH]

The pH of the composition according to the present invention may be from3 to 9, preferably from 3.5 to 8.5, and more preferably from 4 to 8.

At a pH of from 3 to 9, the (a) particle can be very stable.

The pH of the composition according to the present invention may beadjusted by adding at least one alkaline agent and/or at least one acidother than the (d) acid to be incorporated into the (a) particle. The pHof the composition according to the present invention may also beadjusted by adding at least one buffering agent.

(Alkaline Agent)

The composition according to the present invention may comprise at leastone alkaline agent. Two or more alkaline agents may be used incombination. Thus, a single type of alkaline agent or a combination ofdifferent types of alkaline agents may be used.

The alkaline agent may be an inorganic alkaline agent. It is preferablethat the inorganic alkaline agent be selected from the group consistingof ammonia; alkaline metal hydroxides; alkaline earth metal hydroxides;alkaline metal phosphates and monohydrogenophosphates such as sodiumphosphate or sodium monohydrogen phosphate.

As examples of the inorganic alkaline metal hydroxides, mention may bemade of sodium hydroxide and potassium hydroxide. As examples of thealkaline earth metal hydroxides, mention may be made of calciumhydroxide and magnesium hydroxide. As an inorganic alkaline agent,sodium hydroxide is preferable.

The alkaline agent may be an organic alkaline agent. It is preferablethat the organic alkaline agent be selected from the group consisting ofmonoamines and derivatives thereof; diamines and derivatives thereof;polyamines and derivatives thereof; basic amino acids and derivativesthereof; oligomers of basic amino acids and derivatives thereof;polymers of basic amino acids and derivatives thereof; urea andderivatives thereof; and guanidine and derivatives thereof.

As examples of the organic alkaline agents, mention may be made ofalkanolamines such as mono-, di- and tri-ethanolamine, andisopropanolamine; urea, guanidine and their derivatives; basic aminoacids such as lysine, ornithine or arginine; and diamines such as thosedescribed in the structure below:

wherein R denotes an alkylene such as propylene optionally substitutedby a hydroxyl or a C₁-C₄ alkyl radical, and R₁, R₂, R₃ and R₄independently denote a hydrogen atom, an alkyl radical or a C₁-C₄hydroxyalkyl radical, which may be exemplified by 1,3-propanediamine andderivatives thereof. Arginine, urea and monoethanolamine are preferable.

The alkaline agent(s) may be used in a total amount of from 0.1 to 20%by weight, preferably from 0.2 to 10% by weight, more preferably from0.3 to 5% by weight, relative to the total weight of the composition,depending on their solubility.

(Acid)

The composition according to the present invention may comprise at leastone acid other than the (d) acid to be incorporated into the (a)particle. Two or more acids may be used in combination. Thus, a singletype of acid or a combination of different types of acids may be used.

As the acid, mention may be made of any inorganic or organic acids,preferably inorganic acids, which are commonly used in cosmeticproducts. A monovalent acid and/or a polyvalent acid may be used. Amonovalent acid such as citric acid, lactic acid, sulfuric acid,phosphoric acid and hydrochloric acid (HCl) may be used. HCl ispreferable.

The acid(s) may be used in a total amount of from 0.1 to 15% by weight,preferably from 0.2 to 10% by weight, more preferably from 0.3 to 5% byweight, relative to the total weight of the composition, depending ontheir solubility.

(Buffering Agent)

The composition according to the present invention may comprise at leastone buffering agent. Two or more buffering agents may be used incombination. Thus, a single type of buffering agent or a combination ofdifferent types of buffering agents may be used.

As the buffering agent, mention may be made of an acetate buffer (forexample, acetic acid+sodium acetate), a phosphate buffer (for example,sodium dihydrogen phosphate+di-sodium hydorogen phosphate), a citratebuffer (for example, citric acid+sodium citrate), a borate buffer (forexample, boric acid+sodium borate), a tartrate buffer (for example,tartaric acid+sodium tartrate dihydrate), Tris buffer (for example,tris(hydroxymethyl)aminomethane), Hepes buffer(4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[Optional Additives]

The composition according to the present invention may comprise, inaddition to the aforementioned components, components typically employedin cosmetics, specifically, surfactants or emulsifiers, hydrophilicthickeners, organic non-volatile solvents, silicones and siliconederivatives other than the (b) oil, natural extracts derived fromanimals or vegetables, waxes, and the like, within a range which doesnot impair the effects of the present invention.

The composition according to the invention may also comprise at leastone fatty acid. The fatty acid may be useful for controlling thehydrophobicity of the (a) particles which may influence theencapsulation ability of the (a) particles, depending on the type of the(b) oil.

The composition according to the present invention may comprise theabove optional additive(s) in an amount of from 0.01 to 50% by weight,preferably from 0.05 to 30% by weight, and more preferably from 0.1 to10% by weight, relative to the total weight of the composition.

However, it is preferable that the composition according to the presentinvention include a very limited amount of surfactant(s) oremulsifier(s). The amount of the surfactant(s) or emulsifier(s) in thecomposition according to the present invention may be 0.1% by weight orless, preferably 0.01% by weight or less, and more preferably 0.001% byweight or less, relative to the total weight of the composition. It isin particular preferable that the composition according to the presentinvention include no surfactant or emulsifier.

[Composition]

Since the composition according to the present invention comprises atleast one (b) oil, the composition according to the present inventioncan comprise at least one fatty phase.

On the other hand, since the composition according to the presentinvention comprises (c) water, the composition according to the presentinvention can comprise at least one aqueous phase.

The aqueous phase may comprise at least one C₂-C₆ monohydric alcohol.Two or more C₂-C₆ monohydric alcohols may be used in combination.

The C₂-C₆ monohydric alcohol suitable for the present invention maycomprise from 2 to 5 carbon atoms, preferably from 2 to 4 carbon atoms,such as ethanol, isopropanol, propanol or butanol.

Ethanol and isopropanol, and preferably ethanol, are very particularlysuitable for the present invention.

The amount of the C₂-C₆ monohydric alcohol in the composition accordingto the present invention may be 20% by weight or less, preferably 15% byweight or less, and more preferably 10% by weight or less, relative tothe total weight of the composition. On the other hand, the amount ofthe C₂-C₆ monohydric alcohol in the composition according to the presentinvention is 5% by weight or more, preferably 6% by weight or more, andmore preferably 7% by weight or more, relative to the total weight ofthe composition. For example, the amount of the C₂-C₆ monohydric alcoholmay be from 5% to 20% by weight, preferably from 6% to 15% by weight,and more preferably from 7% to 10% by weight, in relation to the totalweight of the composition.

The aqueous phase may comprise polyhydric alcohols containing 2 to 8carbon atoms such as propylene glycol, ethylene glycol, 1,3-butyleneglycol, dipropylene glycol, diethylene glycol, pentyleneglycol,hexyleneglycol, glycerin, and mixtures thereof.

The amount of the polyhydric alcohol(s) such as glycols, if present, inthe aqueous phase according to the present invention may range from 0.1to 15% by weight, preferably from 0.5 to 12% by weight, and morepreferably from 1 to 8% by weight, relative to the total weight of thecomposition.

The composition according to the present invention can be in the form ofan emulsion, an O/W emulsion or a W/O emulsion. It is preferable thatthe composition according to the present invention be in the form of anO/W emulsion, because it can provide a fresh sensation due to the (c)water which forms the outer phase thereof.

It is more preferable that the amount of the surfactant(s) oremulsifier(s) in the emulsion, in particular an O/W emulsion, be 0.1% byweight or less, preferably 0.01% by weight or less, and more preferably0.001% by weight or less, relative to the total weight of thecomposition, because the surfactant(s) may negatively affectwater-resistance. It is in particular preferable that the emulsion, inparticular an O/W emulsion include no surfactant or emulsifier.

The composition according to the present invention may be intended to beused as a cosmetic composition. Thus, the cosmetic composition accordingto the present invention may be intended for application onto a keratinsubstance. Keratin substance here means a material containing keratin asa main constituent element, and examples thereof include the skin,scalp, nails, lips, hair, and the like. Thus, it is preferable that thecosmetic composition according to the present invention be used for acosmetic process for the keratin substance, in particular skin.

Thus, the cosmetic composition according to the present invention may bea skin cosmetic composition, preferably a skin care composition or askin makeup composition, in particular a composition for protecting skinfrom UV and/or pollutants in the air.

The composition according to the present invention can be prepared bymixing the above essential and optional ingredients in accordance withany of the processes which are well known to those skilled in the art.

The composition according to the present invention can be prepared bysimple or easy mixing with a conventional mixing means such as astirrer. Thus, strong shearing by, for example, a homogenizer is notnecessary. Also, heating is not necessary.

[Film]

The composition according to the present invention can be used foreasily preparing a film. The (a) particles can aggregate and integrateinto a continuous film.

Thus, the present invention also relates to a process for preparing afilm, preferably a cosmetic film, with a thickness of, preferably morethan 0.1 μm, more preferably 1.5 μm or more, and even more preferably 2μm or more, comprising:

applying onto a substrate, preferably a keratin substrate, morepreferably skin, the composition according to the present invention; and

drying the composition.

The upper limit of the thickness of the film according to the presentinvention is not limited.

Thus, for example, the thickness of the film according to the presentinvention may be 1 mm or less, preferably 500 μm or less, morepreferably 300 μm or less, and even more preferably 100 μm or less.

Since the process for preparing a film according to the presentinvention includes the steps of applying the composition according tothe present invention onto a substrate, preferably a keratin substrate,and more preferably skin, and of drying the composition, the processaccording to the present invention does not need any spin coating orspraying, and therefore, it is possible to easily prepare even arelatively thick film. Thus, the process for preparing a film accordingto present invention can prepare a relatively thick film without anyspecial equipment such as spin coaters and spraying machines.

Even if the film according to the present invention is relatively thick,it is still thin and may be transparent, and therefore, may not be easyto perceive. Thus, the film according to the present invention can beused preferably as a cosmetic film.

If the substrate is not a keratin substrate such as skin, thecomposition according to the present invention may be applied onto asubstrate made from any material other than keratin. The materials ofthe non-keratinous substrate are not limited. Two or more materials maybe used in combination. Thus, a single type of material or a combinationof different types of materials may be used. In any event, it ispreferable that the substrate be flexible or elastic.

If the substrate is not a keratin substrate, it is preferable that thesubstrate be water-soluble, because it is possible to leave the filmaccording to the present invention by washing the substrate with water.As examples of the water-soluble materials, mention may be made ofpoly(meth) acrylic acids, polyethyleneglycols, polyacrylamides,polyvinylalcohol (PVA), starch, celluloseacetates, and the like. PVA ispreferable.

If the non-keratinous substrate is in the form of a sheet, it may have athickness of more than that of the film according to the presentinvention, in order to ease the handling of the film attached to thesubstrate sheet. The thickness of the non-keratinous substrate sheet isnot limited, but may be from 1 μm to 5 mm, preferably from 10 μm to 1mm, and more preferably from 50 to 500 μm.

It is more preferable that the film according to the present inventionbe releasable from the non-keratinous substrate. The mode of release isnot limited. Therefore, the film according to the present invention maybe peeled from the non-keratinous substrate, or released by thedissolution of the substrate sheet into a solvent such as water.

The present invention also relates to:

-   (1) A film, preferably a cosmetic film, with a thickness of,    preferably more than 0.1 μm, more preferably 1.5 μm or more, and    even more preferably 2 μm or more, prepared by a process comprising:    -   applying onto a substrate, preferably a keratin substrate, and        more preferably skin, the composition according to the present        invention; and    -   drying the composition,

and

-   (2) A film, preferably a cosmetic film, with a thickness of,    preferably more than 0.1 μm, more preferably 1.5 μm or more, and    even more preferably 2 μm or more, comprising:    -   at least one cationic polymer and at least one anionic polymer,    -   at least one cationic polymer and at least one amphoteric        polymer,    -   at least one anionic polymer and at least one amphoteric        polymer, or    -   at least one amphoteric polymer;    -   at least one non-polymeric acid having two or more pKa values or        salt(s) thereof or    -   at least one non-polymeric base having two or more pKb values or        salt(s) thereof,    -   and    -   at least one oil.

The above explanations regarding the cationic and anionic polymers aswell as the above oil can apply to those in the above film (1) and (2).

The film thus obtained above can be self-standing. The term“self-standing” here means that the film can be in the form of a sheetand can be handled as an independent sheet without the assistance of asubstrate or support. Thus, the term “self-standing” may have the samemeaning as “self-supporting”.

It is preferable that the film according to the present invention behydrophobic.

The term “hydrophobic” in the present specification means that thesolubility of the polymer in water (preferably with a volume of 1 liter)at from 20 to 40° C., preferably from 25 to 40° C., and more preferablyfrom 30 to 40° C. is less than 10% by weight, preferably less than 5% byweight, more preferably less than 1% by weight, and even more preferablyless than 0.1% by weight, relative to the total weight of the polymer.It is most preferable that the polymer is not soluble in water.

If the film according to the present invention is hydrophobic, the filmcan have water-resistant properties, and therefore, it can remain on akeratin substrate such as skin even if the surface of the keratinsubstrate is wet due to, for example sweat and rain. Thus, when the filmaccording to the present invention provides any cosmetic effect, thecosmetic effect can last a long time.

On the other hand, the film according to the present invention can beeasily removed from a keratin substrate such as skin under alkalineconditions such as a pH of from 8 to 12, preferably from 9 to 11.Therefore, the film according to the present invention is difficult toremove with water, while it can be easily removed with a soap which canprovide such alkaline conditions.

The film according to the present invention may comprise at least onebiocompatible and/or biodegradable polymer layer. Two or morebiocompatible and/or biodegradable polymers may be used in combination.Thus, a single type of biocompatible and/or biodegradable polymer or acombination of different types of biocompatible and/or biodegradablepolymers may be used.

The term “biocompatible” polymer in the present specification means thatthe polymer does not have excess interaction between the polymer andcells in the living body including the skin, and the polymer is notrecognized by the living body as a foreign material.

The term “biodegradable” polymer in the present specification means thatthe polymer can be degraded or decomposed in a living body due to, forexample, the metabolism of the living body itself or the metabolism ofthe microorganisms which may be present in the living body. Also, thebiodegradable polymer can be degraded by hydrolysis.

If the film according to the present invention includes a biocompatibleand/or biodegradable polymer, it is less irritable or not irritable tothe skin, and does not cause any rash. In addition, due to the use of abiocompatible and/or biodegradable polymer, the cosmetic sheet accordingto the present invention can adhere well to the skin.

The film according to the present invention can be used for cosmetictreatments of keratin substances, preferably skin, in particular theface. The film according to the present invention can be in any shape orform. For example, it can be used as a full-face mask sheet, or a patchfor a part of the face such as the cheek, nose, and around the eyes.

If the film according to the present invention includes at least onehydrophilic or water-soluble UV filter, it can provide UV shieldingeffects derived from the hydrophilic or water-soluble UV filter.Normally, a hydrophilic or water-soluble UV filter can be removed fromthe surface of a keratinous substrate such as skin by water such assweat and rain. However, since the hydrophilic or water-soluble UVfilter is included in the film according to the present invention, it isdifficult for the hydrophilic or water-soluble UV filter to be removedby water, thereby resulting in long-lasting UV shielding effects.

[Cosmetic Process and Use]

The present invention also relates to:

a cosmetic process for a keratin substrate such as skin, comprising:applying to the keratin substrate the composition the present invention;and drying the composition to form a cosmetic film on the keratinsubstrate; and

a use of the composition according to the present invention for thepreparation of a cosmetic film on a keratin substrate such as skin.

The cosmetic process here means a non-therapeutic cosmetic method forcaring for and/or making up the surface of a keratin substrate such asskin.

In both the above process and use, the above cosmetic film is resistantto water with a pH of 7 or less, and is removable with water with a pHof more than 7, preferably 8 or more, and more preferably 9 or more.

In other words, the above cosmetic film can be water-resistant underneutral or acidic conditions such as a pH of 7 or less, preferably in arange of 6 or more and 7 or less, and more preferably in a range of 5 ormore and 7 or less, while the above cosmetic film can be removed underalkaline conditions such as a pH of more than 7, preferably 8 or more,and more preferably 9 or more. The upper limit of the pH is preferably13, more preferably 12, and even more preferably 11.

Accordingly, the above cosmetic film can be water-resistant, andtherefore, it can remain on a keratin substrate such as skin even if thesurface of the keratin substrate is wet due to, for example sweat andrain. On the other hand, the above cosmetic film can be easily removedfrom a keratin substrate such as skin under alkaline conditions.Therefore, the film according to the present invention is difficult toremove with water, while it can be easily removed with a soap which canprovide alkaline conditions.

If the above cosmetic film includes a UV filter which may be present inthe composition according to the present invention, the above cosmeticfilm can protect a keratin substrate such as skin from UV rays, therebylimiting the darkening of the skin, improving the colour and uniformityof the complexion, and/or treating aging of the skin.

Furthermore, the above cosmetic film may have cosmetic effects such asabsorbing or adsorbing malodor, changing the appearance of a keratinsubstrate such as skin, changing the feel to the touch of the keratinsubstrate, and/or protecting the keratin substrate from, for example,dirt or pollutant, due to the properties of the polyion complexparticles in the cosmetic film, even if the cosmetic film does notinclude any cosmetic active ingredient.

In addition, the above cosmetic film may immediately change or modifythe appearance of the skin by changing light reflection on the skin andthe like, even if the cosmetic film does not include any cosmetic activeingredient. Therefore, it may be possible for the above cosmetic film toconceal skin defects such as pores or wrinkles. Further, the abovecosmetic film may immediately change or modify the feel to the touch ofthe skin by changing the surface roughness on the skin and the like.Furthermore, the above cosmetic film may immediately protect the skin bycovering the surface of the skin and shielding the skin, as a barrier,from environmental stresses such as pollutants, contaminants and thelike.

The above cosmetic effects can be adjusted or controlled by changing thechemical composition, the thickness and/or the surface roughness of theabove cosmetic film.

If the above cosmetic film includes at least one additional cosmeticactive ingredient other than the (b) oil, the cosmetic film can havecosmetic effects provided by the additional cosmetic activeingredient(s). For example, if the cosmetic film includes at least onecosmetic active ingredient selected from anti-aging agents, anti-sebumagents, deodorant agents, anti-perspirant agents, whitening agents and amixture thereof, the cosmetic film can treat the aging of the skin,absorbing sebum on the skin, controlling odors on the skin, controllingperspiration on the skin, and/or whitening of the skin.

It is also possible to apply a makeup cosmetic composition onto thecosmetic sheet according to the present invention after being appliedonto the skin.

EXAMPLES

The present invention will be described in a more detailed manner by wayof examples. However, they should not be construed as limiting the scopeof the present invention.

[Preparation of Polyion Complex Particle 1]

1.50 g of a 10 wt % aqueous solution of carboxymethylcellulose (CMC) asa polyanion, 16.76 g of a 25 wt % aqueous solution of polylysine (PLYS)as a polycation, 0.58 g of a 40 wt % aqueous solution of sodiumstyrene/maleic acid copolymer (SMA) as a polyanion, 0.30 g ofphenylalanine, 0.50 g of phenoxyethanol, and 50.06 g of water were mixedby using a stirrer. While stirring, 30.30 g of an aqueous solutioncontaining 33 wt % of terephthalylidene dicamphor sulfonic acid (MexorylSX) was added to the above mixture. With the decrease of the pH of themixture thus obtained, polyion complex gel particles (PGP) were formed.Thus, a stable PGP dispersion was successfully prepared. The final pH ofthe PGP dispersion was about 4-4.5. The number average particle size ofthe obtained particle was 800 nm.

The materials used to prepare the PGP dispersion according to Example 1are shown in Table 1. The numerical values for the amounts of theingredients shown in Table 1 are all based on g.

TABLE 1 amount Carboxymethylcellulose (CMC) (MW 100,000) 1.50Poly-ε-lysine (PLYS) (MW 5000) 16.76 Phenylalanine 0.30 SodiumStyrene/Maleic Acid Copolymer (SMA) 0.58 Phenoxyethanol 0.50Terephthalylidene Dicamphor Sulfonic Acid (MSX) 30.30 Water qsp 100

Mexoryl SX:

(Preparation of Emulsion)

An emulsion was prepared by using the PGP dispersion prepared as above.Each of the oily ingredients shown in Table 2 was added to the PGPdispersion, and mixed with a homogenizer at 2500 rpm for 20 minutesunder the conditions that the amount of the PGP was 15% by weightrelative to the total weight of the emulsion. The amount of each oilyingredient is also shown in Table 2. The numerical values for theamounts of the ingredients shown in Table 2 are all based on “% byweight”.

TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Mineral Oil 1020 29.01 — — — — — Ethylenediamine/Stearyl — — 0.13 — — — — — DimerDilinoleate Copolymer Isononyl Isononanoate — — — 20 29.14 — — —Dimethicone — — — — — 20 29.14 — Caprylic/Capric — — — — — — — 29.14Triglyceride Stability Very Very Stable Very Very Stable Stable VeryStable Stable Stable Stable Stable

(Evaluation 1)

The emulsions according to Examples 1 to 8 were stored for 1 month. Theaspect of each emulsion was visually observed, and evaluated inaccordance with the following criteria.

Very Stable: No phase separation was observed.

Stable: Slight phase separation was observed, but the aspect was almosthomogeneous as a whole.

The results are shown in Table 2.

Table 2 shows that PGP can be used for preparing stable emulsions with avariety of oils. By using PGP, emulsions can be prepared without anysurfactant. At least, up to about 30% by weight of oil can be used, butit may be preferable that the amount of oil be about 30% by weight orless.

Table 2 also shows that both polar and non-polar oils can be used toprepare emulsions. It may be preferable to use polar oils such asisononyl isononanoate and caprylic/capric triglyceride in terms ofstability of emulsions. However, by combining with an oil gelling agentsuch as ethylenediamine/stearyl dimer dilinoleate copolymer, non-polaroil such as mineral oil can also be very stably emulsified.

(Evaluation 2)

An adequate small amount of pyranine and nile red were added to theemulsions according to Examples 1 to 8. Pyramine was used as afluorescent marker for the aqueous phase of the emulsions. Nile red wasused as a fluorescent marker for the oil phase of the emulsions.

The emulsions according to Examples 1 to 8 were observed with afluorescent microscope. It was observed that oil was encapsulated withcapsules made from the PGP. In other words, oil globules were coatedwith a thin film or layer made from the PGP. FIG. 1 shows oil globulesencapsulated with capsules made from the PGP according to Example 1.Thus, the emulsions according to Examples 1 to 8 were a type of O/Wemulsion.

It was found that the PGP is located on the interface between water andoil, as the PGP is amphiphilic and insoluble in water and oil, and thatPGP encapsulation can be easily performed by a process of simply mixinga PGP dispersion and oil(s) without heating or strongly shearing.

[Preparation of Polyion Complex Particle 2]

Example 9

0.02 g of carboxymethylcellulose and 0.2 g of vegetable chitosan weredissolved into 60 g of water, and pH was adjusted to 2.5 by 4 wt % HCLaqueous solution. 1.5 g of an aqueous solution (10 wt %) of arginine wasadded to this mixture until pH reached 6.4. During the pH increase ofthe mixture, cationic polyion complex particles (cationic PGP), whichwere composed of carboxymethylcellulose (polyanion), chitosan(polycation) and arginine (cationic crosslinker), were successfullyprepared.

The diameter of the cationic PGP was about 15 nm, and the ζ potential ofthe cationic PGP was 30 mV.

The cationic PGP dispersion according to Example 9 was stable for 2weeks at room temperature. Thus, no precipitates were visually observedfor 2 weeks.

Example 10

0.05 g of carboxymethylcellulose and 0.2 g of vegetable chitosan weredissolved into 60 g of water, and pH was adjusted to 1.8 by 4 wt % HClaqueous solution. 3 g of an aqueous solution (10 wt %) of arginine wasadded to this mixture until pH reached 4.9. During the pH increase ofthe mixture, particles of cationic PGP, which were composed ofcarboxymethylcellulose (polyanion), chitosan (polycation) and arginine(cationic crosslinker), were successfully prepared.

The diameter of the cationic PGP was about 370 nm, and the ζ potentialof the cationic PGP was 6 mV.

The cationic PGP dispersion according to Example 1 was stable for 2weeks at room temperature. Thus, no precipitates were visually observedfor 2 weeks.

[Preparation of Crosslinked Polyampholyte Particle 1]

As a polyanion, a 10 wt % aqueous solution of carboxymethylcellulose(CMC) was used. As a polycation, a 25 wt % aqueous solution ofpolylysine (PLYS) was used. As a polyampholyte, a 20.54 wt % aqueoussolution of polyquaternium-53 was used.

For Examples 11-16, in accordance with the composition shown in Table 3shown below, the ingredients shown in Table 3 except forterephthalylidene dicamphor sulfonic acid (Mexoryl SX: MSX) were addedinto a beaker, heated at 70° C., and mixed with a stirrer, such that theamount of each of the ingredients was as shown in Table 3. Then, anaqueous solution containing 33 wt % of MSX was added to the abovemixture such that the amount of MSX was as shown in Table 3. With thedecrease of the pH of the mixture thus obtained, crosslinkedpolyampholyte particles (CARP) were formed. Thus, a stable CARPdispersion was successfully prepared. The number average particle sizeof the obtained particle was 1 μm. The numerical values shown in Table 3are all based on “% by weight” of the active material in eachingredient.

TABLE 3 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Carboxymethylcellulose(CMC) 1.00 — — — — 1.00 (MW 100,000) Poly-ε-lysine (PLYS) (MW — — — 3.773.77 — 5000) Polyquaternium-53 5.00 5.00 5.00 5.00 5.00 5.00Phenylalanine 0.30 — — — — — Terephthalylidene Dicamphor 2.90 0.99 1.306.60 7.90 2.90 Sulfonic Acid (MSX) Water qsp 100 qsp 100 qsp 100 qsp 100qsp 100 qsp 100 CARP Formation Good Good Good Good Good Good EmulsionStability Stable Stable Stable Stable Stable Stable Water ResistivityGood Good Good Good Good Good

[Preparation of Crosslinked Polyampholyte Particle 2]

As a polyanion, a 10 wt % aqueous solution of carboxymethylcellulose(CMC) was used. As a polyampholyte, a 9.25 wt % aqueous solution ofpolyquaternium-39 was used.

For Examples 17-21, in accordance with the composition shown in Table 4shown below, the ingredients shown in Table 4 except forterephthalylidene dicamphor sulfonic acid (Mexoryl SX: MSX) and/orphytic acid were added into a beaker, heated at 70° C., and mixed with astirrer, such that the amount of each of the ingredients was as shown inTable 4. Then, an aqueous solution containing 33 wt % of MSX and/orphytic acid was added to the above mixture such that the amount of MSXand/or phytic acid was as shown in Table 4. With the decrease of the pHof the mixture thus obtained, crosslinked polyampholyte particles (CARP)were formed. Thus, a stable CARP dispersion was successfully prepared.The number average particle size of the obtained particle was 1 μm. Thenumerical values shown in Table 4 are all based on “% by weight” of theactive material in each ingredient.

TABLE 4 Ex. Ex. Ex. Ex. Ex. 17 18 19 20 21 Carboxymethylcellulose 1.00 —— 1.00 — (CMC) (MW 100,000) Polyquaternium-39 5.00 1.35 1.35 2.50 3.38Phenylalanine 0.30 0.27 — 0.30 — Sodium Styrene/ 0.20 — — — — MaleicAcid Copolymer (SMA) Terephthalylidene — 0.46 0.46 0.99 0.46 DicamphorSulfonic Acid (MSX) Phytic Acid 2.50 — — 5.00 — Water qsp qsp qsp qspqsp 100 100 100 100 100 CARP Formation Good Good Good Good Good EmulsionStability Stable Stable Stable Stable Stable Water Resistivity Good GoodGood Good Good

(Evaluation 3)

The aspect of the compositions according to Examples 11-21 was observedwith microscopy, and evaluated in accordance with the followingcriteria.

Good: Particles were formed.

Poor: Particles were not formed.

The results are shown in the “CARP Formation” line in Tables 3 and 4.

[Preparation of Emulsion]

An emulsion was prepared by using the CARP dispersion prepared as above.Each of the oily ingredients shown below was added to the CARPdispersion, and mixed with a homogenizer at 2500 rpm for 20 minutesunder the conditions that the amount of the CARP was 15% by weightrelative to the total weight of the emulsion. The amount of each oilyingredient is also shown below. The numerical values for the amounts ofthe ingredients shown below are all based on “% by weight”.

ETHYLHEXYL TRIAZONE 1.46 OCTOCRYLENE 0.50 BIS-ETHYLHEXYLOXYPHENOL 0.49METHOXYPHENYL TRIAZINE BUTYL METHOXYDIBENZOYLMETHANE 1.40 Cl2-15 AlkylBenzoate 1.01 ETHYLENEDIAMINE/STEARYL DIMER 0.07 DILINOLEATE COPOLYMERISONONYL ISONONANOATE 5.00

(Evaluation 4)

The emulsions prepared with the CARP dispersion according to Examples11-21 were stored at room temperature for 1 month. The aspect of each ofthe emulsion was visually observed, and evaluated in accordance with thefollowing criteria.

Stable: no phase separation was observed, or slight phase separation wasobserved but the aspect was almost homogeneous as a whole.

Unstable: complete phase separation was observed.

The results are shown in “Emulsion Stability” line in Tables 3 and 4.

(Evaluation 5)

50 mg of the emulsion prepared with the CARP dispersion according toeach of Examples 11-21 was applied onto a surface of apolymethylmethacrylate (PMMA) plate (HELIOPLATE HD6) and dried at roomtemperature for 1 hour.

After drying, the PMMA plate was dipped into a calcium chloride solution(0.14 g/l) at room temperature for 15 minutes.

After dipping, the PMMA plate was pulled up, and dried for 1 hour. Thesurface of the PMMA plate was visually observed, and evaluated inaccordance with the following criteria.

Good: A film was present on the PMMA plate.

Poor: A film was not present on the PMMA plate.

The results are shown in the “Water Resistivity” line in Tables 3 and 4.The thickness of the obtained film was 1 m.

[Preparation of Emulsion]

As a polyampholyte, a 20.54 wt % aqueous solution of polyquaternium-53was used.

In accordance with the composition shown in Table 5 shown below, theabove ingredient and water were added into a beaker, heated at 70° C.,and mixed with a stirrer, such that the amount of each of theingredients was as shown in Table 5. Then, an aqueous solutioncontaining 33 wt % of terephthalylidene dicamphor sulfonic acid (MexorylSX) was added to the above mixture such that the amount of Mexory SX wasas shown in Table 5. With the decrease of the pH of the mixture thusobtained, crosslinked polyampholyte particles (CARP) were formed. Thus,a stable CARP dispersion was successfully prepared. The numerical valuesshown in Table 5 are all based on “% by weight” of the active materialin each ingredient.

Then, the oily ingredients shown in Table 5 (cf. shaded lines) wereadded to the CARP dispersion, and mixed with a homogenizer at 6000 rpmfor 20 minutes to prepare an emulsion according to Example 22. Theamount of each of the oily ingredients is also shown in Table 5. Thenumerical values for the amounts of the ingredients shown in Table 5 areall based on “% by weight” of the active material in each ingredient.

TABLE 5 Ex. 22 Polyquaternium-53 10.00 Water 73.31 TerephthalylideneDicamphor Sulfonic Acid (MSX) 2.60 ETHYLHEXYL TRIAZONE 1.46 OCTOCRYLENE0.50 BIS-ETHYLHEXYLOXYPHENOL 0.49 METHOXYPHENYL TRIAZINE BUTYLMETHOXYDIBENZOYLMETHANE 1.40 C12-15 Alkyl Benzoate 1.01ETHYLENEDIAMINE/STEARYL DIMER 0.07 DILINOLEATE COPOLYMER ISONONYLISONONANOATE 5.00

(Evaluation 6)

An adequate small amount of pyranine and nile red were added to theemulsions according to Example 22. Pyramine was used as a fluorescentmarker for the aqueous phase of the emulsion. Nile red was used as afluorescent marker for the oil phase of the emulsion.

The emulsion according to Example 22 was observed with a fluorescentmicroscope. It was observed that oil was encapsulated with capsules madefrom the CARP. In other words, oil globules were coated with a thin filmor layer made from the CARP. Thus, the emulsion according to Example 22is a type of O/W emulsion.

It was found that the CARP is located on the interface between water andoil, as the CARP is amphiphilic and insoluble in water and oil, and thatCARP encapsulation can be easily performed by a process of simply mixinga CARP dispersion and oil(s) without heating or strongly shearing.

1. A composition, preferably a cosmetic composition, and more preferablya skin cosmetic composition, comprising: (a) at least one particle,comprising at least one cationic polymer and at least one anionicpolymer, at least one cationic polymer and at least one amphotericpolymer, at least one anionic polymer and at least one amphotericpolymer, or at least one amphoteric polymer, and at least onenon-polymeric acid having two or more pKa values or salt(s) thereof orat least one non-polymeric base having two or more pKb values or salt(s)thereof; (b) at least one oil; and (c) water.
 2. The compositionaccording to claim 1, wherein a plurality of the (a) particles arepresent at the interface between the (b) oil and the (c) water, or aplurality of the (a) particles form a capsule having a hollow, and the(b) oil is present in the hollow.
 3. The composition according to claim1, wherein the cationic polymer has at least one positively chargeableand/or positively charged moiety selected from the group consisting of aprimary, secondary or tertiary amino group, a quaternary ammonium group,a guanidine group, a biguanide group, an imidazole group, an iminogroup, and a pyridyl group.
 4. The composition according to claim 1,wherein the cationic polymer is selected from the group consisting ofcyclopolymers of alkyldiallylamine and cyclopolymers ofdialkyldiallylammonium such as (co)polydiallyldialkyl ammonium chloride,(co)polyamines such as (co)polylysines and chitosan, cationic(co)polyaminoacids such as collagen, and salts thereof.
 5. Thecomposition according to claim 1, wherein the anionic polymer has atleast one negatively chargeable and/or negatively charged moietyselected from the group consisting of a sulfuric group, a sulfate group,a sulfonic group, a sulfonate group, a phosphoric group, a phosphategroup, a phosphonic group, a phosphonate group, a carboxylic group, anda carboxylate group.
 6. The composition according to claim 1, whereinthe anionic polymer is selected from the group consisting ofpolysaccharides such as alginic acid, hyaluronic acid, and cellulosepolymers, anionic (co)polyaminoacids such as (co)polyglutamic acids,(co)poly(meth)acrylic acids, (co)polyamic acids, (co)polystyrenesulfonate, (co)poly(vinyl sulfates), dextran sulfate, chondroitinsulfate, (co)polymaleic acids, polyfumaric acids, maleic acid(co)polymers, and salts thereof.
 7. The composition according to claim1, wherein the amphoteric polymer has at least one positively chargeableand/or positively charged moiety selected from the group consisting of aprimary, secondary or tertiary amino group, a quaternary ammonium group,a guanidine group, a biguanide group, an imidazole group, an iminogroup, and a pyridyl group, and at least one negatively chargeableand/or negatively charged moiety selected from the group consisting of asulfuric group, a sulfate group, a sulfonic group, a sulfonate group, aphosphoric group, a phosphate group, a phosphonic group, a phosphonategroup, a carboxylic group, and a carboxylate group.
 8. The compositionaccording to claim 1, wherein the amphoteric polymer is selected fromthe group consisting of polyquaternium-22, polyquaternium-39,polyquaternium-53, polyquaternium-64, polyquaternium-51,polyquaternium-61, and mixtures thereof.
 9. The composition according toclaim 1, wherein the amount of the polymer(s), in the composition isfrom 0.001 to 25% by weight, preferably from 0.1 to 20% by weight, andmore preferably from 1 to 15% by weight, relative to the total weight ofthe composition.
 10. The composition according to claim 1, wherein theamount of the non-polymeric acid having two or more pKa values orsalt(s) thereof or non-polymeric base having two or more pKb values orsalt(s) thereof in the composition is from 0.0001 to 30% by weight,preferably from 0.01 to 20% by weight, and more preferably from 0.1 to15% by weight, relative to the total weight of the composition.
 11. Thecomposition according to claim 1, wherein the (a) particle furthercomprises (d) at least one hydrophobic amino acid other than thenon-polymeric acid or base.
 12. The composition according to claim 1,wherein the pH of the composition is from 3 to 9, preferably from 3.5 to8.5, and more preferably from 4 to
 8. 13. The composition according toclaim 1, wherein the amount of the (a) particle in the composition isfrom 0.001 to 60% by weight, preferably from 0.1 to 50% by weight, andmore preferably from 1 to 40% by weight, relative to the total weight ofthe composition.
 14. The composition according to claim 1, wherein the(b) oil is selected from polar oils.
 15. The composition according toclaim 1, wherein the amount of the (b) oil(s) in the composition is from0.01 to 50% by weight, preferably from 0.1 to 40% by weight, and morepreferably from 1 to 35% by weight, relative to the total weight of thecomposition.
 16. The composition according to claim 1, wherein thecomposition is in the form of an emulsion, preferably an O/W emulsion,and more preferably an O/W emulsion comprising 0.1% by weight or less ofsurfactant(s), preferably 0.01% by weight or less of surfactant(s), andmore preferably no surfactant(s).
 17. The composition according to claim1, wherein the composition further comprises (e) at least one oilgelling agent.
 18. A process for preparing a film, preferably a cosmeticfilm, comprising: applying onto a substrate, preferably a keratinsubstrate, and more preferably skin, the composition according to claim1; and drying the composition.
 19. A film, preferably a cosmetic film,prepared by a process comprising: applying onto a substrate, preferablya keratin substrate, and more preferably skin, the composition accordingto claim 1; and drying the composition.
 20. A film, preferably acosmetic film, comprising: at least one cationic polymer and at leastone anionic polymer, at least one cationic polymer and at least oneamphoteric polymer, at least one anionic polymer and at least oneamphoteric polymer, or at least one amphoteric polymer; at least onenon-polymeric acid having two or more pKa values or salt(s) thereof orat least one non-polymeric base having two or more pKb values or salt(s)thereof, and at least one oil.
 21. A cosmetic process for a keratinsubstrate such as skin, comprising applying to the keratin substrate thecomposition according to claim 1; and drying the composition to form acosmetic film on the keratin substrate.
 22. A use of the compositionaccording to claim 1 for the preparation of a cosmetic film on a keratinsubstrate such as skin, wherein the cosmetic film is resistant to waterwith a pH of 7 or less, and is removable with water with a pH of morethan 7, preferably 8 or more, and more preferably 9 or more.